Microbiocides

ABSTRACT

Compounds of the formula (I), in which the substituents are as defined in claim  1  are suitable for use as microbiocides.

This application is a 371 of International Application No.PCT/EP2008/004789 filed Jun. 13, 2008, which claims priority to EP07011797.3 filed Jun. 15, 2007, and EP 08004438.1 filed Mar. 11, 2008,the contents of which are incorporated herein by reference.

The present invention relates to novel microbiocidally active, inparticular fungicidally active, thienyl/benzthienyl ethyl amides. Itfurther relates to intermediates used in the preparation of thesecompounds, to compositions which comprise these compounds and to theiruse in agriculture or horticulture for controlling or preventinginfestation of plants by phytopathogenic microorganisms, preferablyfungi.

Thienyl ethyl amides and their use as fungicides are described in WO2006/108791 and EP-1710237A1. Benzthienyl ethyl amides and their use asfungicides are described in WO 2007/006739.

It has been found that novel thienyl/benzthienyl ethyl amides havemicrobiocidal activity. The present invention thus provides compounds ofthe formula I

wherein

-   A is a 5- or 6-membered heterocyclic ring containing one to three    heteroatoms, each independently selected from oxygen, nitrogen and    sulphur, or a phenyl ring; the heterocyclic ring or the phenyl being    substituted by the groups R₆, R₇ and R₈;-   R₆, R₇ and R₈ are each, independently, hydrogen, halogen, cyano,    nitro, C₁₋₄ alkyl, C₁₋₄ halogenalkyl, C₁₋₄ halogenalkoxy, C₁₋₄    alkoxy(C₁₋₄)alkyl or C₁ halogenalkoxy(C₁₋₄)alkyl, provided that at    least one of R₆, R₇ and R₈ is not hydrogen;-   R₁ and R₂ independently of each other stand for hydrogen, halogen,    C₁-C₄ alkyl or C₁-C₄ halogenalkyl;-   Q is Q₁

-   or Q is Q₂

wherein

-   R₃ is halogen or C₁-C₄ halogenalkyl;-   R₄ is C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl, halogenphenyl    acetynyl or halogenphenyl;-   R₅ is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,    halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl or    halogenphenyl acetynyl;-   R₁₅ is hydrogen or C₃-C₇cycloalkyl;-   and tautomers/isomers/enantiomers of these compounds.

According to the invention, the term “acetynyl”, as used in thedefinition of substituents R₄ and R₅, stands for the group “—C≡C—”. Asexample, C₃ cycloalkyl acetynyl stands for the group

and is present, for example, as substituent R₄ in compound 1.1.

The alkyl groups occurring in the definitions of the substituents can bestraight-chain or branched and are, for example, methyl, ethyl,n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, n-butyl, sec-butyl,iso-butyl or tert-butyl. Alkoxy, alkenyl and alkynyl radicals arederived from the alkyl radicals mentioned. The alkenyl and alkynylgroups can be mono- or di-unsaturated.

The cycloalkyl groups occurring in the definitions of the substituentsare, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl orcycloheptyl.

Halogen is generally fluorine, chlorine, bromine or iodine, preferablyfluorine, bromine or chlorine. This also applies, correspondingly, tohalogen in combination with other meanings, such as halogenalkyl orhalogenalkoxy.

Halogenalkyl groups preferably have a chain length of from 1 to 4 carbonatoms. Halogenalkyl is, for example, fluoromethyl, difluoromethyl,trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl,1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl,difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy,isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy and ethoxy.Halogenalkoxy is, for example, fluoromethoxy, difluoromethoxy,trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy,2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy andtrifluoromethoxy.

Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl,ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl orisopropoxyethyl.

Halogenphenyl is preferably phenyl substituted by 1, 2 or 3 halogenatoms, for example 4-chloro-phenyl.

In the context of the present invention a “5- or 6-membered heterocyclicring containing one to three heteroatoms, each independently selectedfrom oxygen, nitrogen and sulphur” preferably means pyrazolyl(especially pyrazol-4-yl), thiazolyl (especially thiazol-5-yl), pyrrolyl(especially pyrrol-3-yl), 1,2,3 triazolyl, oxazolyl (especiallyoxazol-5-yl), pyridyl (especially pyrid-3-yl) or 2,3dihydro-[1,4]oxathiinyl (especially 2,3 dihydro-[1,4]oxathiin-5-yl).

The compounds of formula I, wherein R₁₅ is hydrogen, can occur indifferent isomeric forms; the invention covers all those isomers andmixtures thereof. The compounds of the formula I may occur in differenttautomeric forms. For example, compounds of formula I exist in thetautomeric forms I_(I) and I_(II):

The invention covers all those tautomeric forms and mixtures thereof.

Preferably R₁₅ is hydrogen. In a preferred group of compounds A is a5-membered heterocyclic ring containing one to three heteroatoms, eachindependently selected from oxygen, nitrogen and sulphur; theheterocyclic ring being substituted by the groups R₆, R₇ and R₈.

Within said preferred group of compounds, further preferably A is A₁

in which

-   R₁₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,    C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl or    C₁-C₄halogenalkoxy-C₁-C₄alkyl;-   R₁₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,    C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl; and-   R₁₈ is hydrogen, halogen or cyano;-   or A is A₂

in which

-   R₂₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,    C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl or    C₁-C₄halogenalkoxy-C₁-C₄alkyl; and-   R₂₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,    C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl;-   or A is A₃

in which

-   R₃₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,    C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl or    C₁-C₄halogenalkoxy-C₁-C₄alkyl;-   R₃₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,    C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl; and-   R₃₈ is hydrogen, halogen or cyano;-   or A is A₄

in which

-   R₄₆ and R₄₇ independently of one another are halogen, cyano, nitro,    C₁-C₄alkyl, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy,    C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl.

Within said preferred group of compounds, further preferably A is A₁.

Within said preferred group of compounds, further preferably A is A₂.

Within said preferred group of compounds, further preferably A is A₃.

Within said preferred group of compounds, further preferably A is A₄.

In another preferred group of compounds A is a phenyl ring or a6-membered heterocyclic ring containing one to three heteroatoms, eachindependently selected from oxygen, nitrogen and sulphur; the phenylring or the heterocyclic ring being substituted by the groups R₆, R₇ andR₈.

Within said preferred group of compounds, further preferably A is A₅

in which

-   R₅₆ is halogen, C₁-C₄halogenalkyl, C₁-C₄halogenalkoxy, or    C₁-C₄halogenalkoxy-C₁-C₄alkyl;-   or A is A₆

in which

-   R₆₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,    C₁-C₄alkoxy-C₁-C₄alkyl or C₁-C₄halogenalkoxy-C₁-C₄alkyl;-   or A is A₇

in which

-   R₇₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl.

Within said preferred group of compounds, further preferably A is A₅.

Within said preferred group of compounds, further preferably A is A₆.

Within said preferred group of compounds, further preferably A is A₇.

In a particular preferred group of compounds A is A₁, wherein R₁₈ ishydrogen. In another particular preferred group of compounds A is A₁,wherein R₁₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl, preferablyC₁-C₄halogenalkyl; R₁₇ is C₁-C₄alkyl; and R₁₈ is hydrogen or halogen,preferably hydrogen.

In another particular preferred group of compounds A is A₂, wherein R₂₆is C₁-C₄alkyl or C₁-C₄halogenalkyl; and R₂₇ is C₁-C₄alkyl.

In yet another particular preferred group of compounds A is A₃, whereinR₃₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl; R₃₇ is C₁-C₄alkyl; and R₃₈ ishydrogen or halogen.

In yet another particular preferred group of compounds A is A₄, whereinR₄₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl; and R₄₇ is C₁-C₄alkyl.

In yet another particular preferred group of compounds A is A₄, whereinR₄₆ halogenmethyl, preferably R₄₆ is selected from CF₃, CF₂H and CFH₂;and R₄₇ is C₁-C₄alkyl.

In yet another particular preferred group of compounds A is A₅, whereinR₅₆ is halogen or C₁-C₄halogenalkyl.

In yet another particular preferred group of compounds A is A₆, whereinR₆₆ is halogen or C₁-C₄halogenalkyl.

In yet another particular preferred group of compounds A is A₇, whereinR₇₆ is C₁-C₄alkyl or C₁-C₄halogenalkyl.

In a preferred group of compounds R₁ is hydrogen or methyl. In oneembodiment, R₁ is hydrogen. In one embodiment, R₁ is methyl.

In a preferred group of compounds R₂ is hydrogen.

In one embodiment Q is Q₁.

In one embodiment Q₁ is Q_(1A)

wherein R₃, R₄ and R₄ are as defined under formula I.

Preferably, Q_(1A) is Q_(1A-1)

wherein R₃, R₄ and R₄ are as defined under formula I. In yet morepreferred compounds within this embodiment, R₃ is halogen, morepreferably chloro or bromo; R₄ is C₃-C₇ cycloalkyl acetynyl, phenylacetynyl, halogenphenyl acetynyl or halogenphenyl; and R₅ hydrogen.These compounds are shown in tables 1 to 6.

In one embodiment Q₁ is Q_(1B)

wherein R₃, R₄ and R₄ are as defined under formula I.

Preferably, Q_(1B) is Q_(1B-1)

wherein R₃, R₄ and R₄ are as defined under formula I.

Preferably, Q_(1B) is Q_(1B-2)

wherein R₃, R₄ and R₄ are as defined under formula I. In yet morepreferred compounds within this embodiment, R₃ is halogen, morepreferably chloro; R₄ is C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl,halogenphenyl acetynyl or halogenphenyl; and R₅ is halogen, even morepreferably chloro. These compounds are shown in tables 7 to 12.

Further preferably, Q_(1B) is Q_(1B-3)

wherein R₃, R₄ and R₄ are as defined under formula I. In yet morepreferred compounds within this embodiment, R₃ is halogen, morepreferably chloro; R₄ is C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl,halogenphenyl acetynyl or halogenphenyl; and R₅ is halogen, even morepreferably chloro. These compounds are also shown in tables 7 to 12.

In one embodiment Q is Q₂. This embodiment is represented by compoundsof tables 13 and 14.

R₃ is preferably halogen, more preferably chloro or bromo.

In a preferred group of compounds R₄ is C₃-C₇ cycloalkyl acetynyl,phenyl acetynyl or halogenphenyl acetynyl.

In another preferred group of compounds R₄ is C₃-C₇ cycloalkyl acetynyl.

In another preferred group of compounds R₄ is halogenphenyl acetynyl,more preferably 4-halogen-phenyl.

In yet another preferred group of compounds R₄ is halogenphenyl, morepreferably 4-halogen-phenyl.

R₅ is preferably hydrogen or halogen.

In one embodiment, R₅ is hydrogen.

In another embodiment R₅ is halogen, preferably chloro.

Compounds of formula I, wherein Q is Q_(1A) and R₂, R₅ and R₁₅ arehydrogen may be prepared according to scheme 1.

A thiophene-2-aldehyde of formula VII, wherein R₃ is as defined underformula I can be reacted with a nitroalkane of the formula R₁CH₂NO₂,wherein R₁ is as defined under formula I to form the nitroalkenes offormula VI, in which R₁ and R₃ are as defined under formula I. Saidreaction is carried out conveniently in the presence of acetic acid andammonium acetate at temperatures between ambient temperature and refluxtemperature.

The nitroalkenes of formula VI can be reduced to the amines of formulaV, wherein R₁ and R₃ are as defined under formula I, by using LiAlH₄ inan ether solvent, such as diethylether or tetrahydrofurane.

Subsequently the amines of formula V can be brominated, for example withbromine in the presence of acetic acid, to the amines of formula IIIA,wherein R₁ and R₃ are as defined under formula I.

The brominated amines of formula IIIA can then be amidated by using thecorresponding acid derivatives, such as acid chlorides of the formulaA-C(O)Cl, wherein A is as defined under formula I, to form thebrominated amides of formula IIA, wherein A, wherein R₁ and R₃ are asdefined under formula I. Said amidations are conveniently carried out inthe presence of a base, such as triethylamine, Hunig base, sodiumbicarbonate, sodium carbonate, potassium carbonate, pyridine orquinoline, but preferably triethylamine, and in a solvent, such asdiethylether, TBME, THF, dichloromethane, chloroform, DMF or NMP, forbetween 10 minutes and 48 hours, preferably 12 to 24 hours, and between0° C. and reflux, preferably 20 to 25° C.

Compounds of the formula IA may be prepared by reacting the brominatedamine of formula IIA with a compound of formula VIA, wherein X ishalogen and n is 1, 2, 3, 4 or 5, preferably 1, using the well knownSuzuki coupling methodology. The Suzuki reaction has also become one ofthe standard methods for the direct coupling of two aromatic ringsystems and is described, for example, in Journal of the AmericanChemical Society 121(41), 9550 (1999) and in Journal für PraktischeChemie 342(4), 334-339 (2000).

Compounds of the formula IB may be prepared by reacting the brominatedamine of formula IIA with an acetynyl compound of the formula IVB,wherein R* is C₃-C₇ cycloalkyl, phenyl or halogenphenyl using the wellknown Sonogashira coupling methodology. The Sonogashira reaction hasbecome one of the standard methods for introducing an alkynyl functioninto unsaturated and aromatic or heteroaromatic molecules. It isreviewed, for example, in the Handbook of Organopalladium Chemistry forOrganic Synthesis Vol. 1, 767-789 (2002); by I. B. Campbell inOrganocopper reagents (IRL-Press, 1994); by K. C. Nicolaou et. al. inAngewandte Chemie Int. Ed., 44, 4442 (2005); by R. Tykwinski et. al.,ibid. 42,1433 (2002); and by A. Zapf et. al. in Topics in Catalysis, 19,101 (2002).

Compounds of formula I, wherein Q is Q_(1B), R₂ is hydrogen and R₅ ischloro may be prepared according to scheme 2.

Thiophene-3-aldehyde (compound of formula XI) can be exhaustivelychlorinated with Cl₂/AlCl₃ according to known methods to generate thetri-chlorinated thiophene aldehyde of formula X.

The compound of formula X can be reacted with a nitroalkane of theformula R₁CH₂NO₂, wherein R₁ is as defined under formula I to form thenitroalkene of formula IX, in which R₁ is as defined under formula I.The nitroalkenes of formula IX can be reduced to the di-chlorinatedamines of formulae VIIIC and VIIID, wherein R₁ is as defined underformula I. Subsequently the amines of formulae VIIIC and VIIID can bebrominated to form the amines of formulae IIIC and IIID, wherein R₁ isas defined under formula I.

The brominated amines of formulae IIIC and IIID can then be amidated byusing the corresponding acid derivatives, such as acid chlorides of theformula A-C(O)Cl, wherein A is as defined under formula I, to form thebrominated amides of formulae IIC and IID, wherein A, wherein R₁ and R₃are as defined under formula I.

Compounds of the formulae IC and ID may be prepared by reacting thebrominated amines of formulae IIC and IID with a compound of formulaVIA, wherein X is halogen and n is 1, 2, 3, 4 or 5, preferably 1, viathe Suzuki reaction.

Suitable reaction conditions for the formation of the compounds offormulae VIIIC, VIIID, IIIC, IIID, IIIC, IIID, IC and ID are asdescribed for scheme 1 above.

Compounds of formula IE and IF

wherein A and R₁ are as defined under formula I and R* is C₃-C₇cycloalkyl, phenyl or halogenphenyl, can be formed from compounds offormula IIC and IID via the Sonogashira reaction as described for scheme1 above.

Compounds of formula I, wherein Q is Q₂, R₂ is hydrogen and R₃ is chloromay be prepared according to scheme 3.

Benzthiophenes of formula XIII, wherein R₅ is as defined under formulaI, can be prepared from compounds of formula XIV, wherein R₅ is asdefined under formula I, as described in J. Org. Chem. 1996, 61(9),6523-25.

Starting from the benzthiophenes of formula XIII, the compounds offormulae XII, IIIG and IIIG, wherein A, R₁ and R₅ are as defined underformula I, can be prepared as described above for scheme 1.

Compounds of formula IG may be prepared by reacting the brominated amideof formula IIG with a compound of formula VIA or VIB as described abovefor scheme 1 via the Suzuki reaction or Sonogashira reaction.

The compounds of the formulae VII, IVA, IVB, XI and XIV, wherein thesubstituents as described above, and the nitroalkanes of formulaR₁CH₂NO₂, wherein R₁ is as defined under formula I, are known andcommercially available or can be prepared according to theabove-mentioned references or according to methods known in the art.

Compounds of the formula A-C(O)Cl are known and partially commerciallyavailable. They can be prepared analogously as described, for example,in WO 00/09482, WO 02/38542, WO 04/018438, EP-0-589-301, WO 93/11117 andArch. Pharm. Res. 2000, 23(4), 315-323.

Compounds of formula I, wherein R₁₅ is C₃-C₇cycloalkyl can be, forexample, prepared according to the following reaction scheme:

For preparing all further compounds of the formula I functionalizedaccording to the definitions of A, Q, R₁ and R₂, there are a largenumber of suitable known standard methods, such as alkylation,halogenation, acylation, amidation, oximation, oxidation and reduction.The choice of the preparation methods which are suitable are dependingon the properties (reactivity) of the substituents in the intermediates.

The reactions to give compounds of the formula I are advantageouslycarried out in aprotic inert organic solvents. Such solvents arehydrocarbons such as benzene, toluene, xylene or cyclohexane,chlorinated hydrocarbons such as dichloromethane, trichloromethane,tetrachloromethane or chlorobenzene, ethers such as diethyl ether,ethylene glycol dimethyl ether, diethylene glycol dimethyl ether,tetrahydrofuran or dioxane, nitriles such as acetonitrile orpropionitrile, amides such as N,N-dimethylformamide, diethylformamide orN-methylpyrrolidinone. The reaction temperatures are advantageouslybetween −20° C. and +120° C. In general, the reactions are slightlyexothermic and, as a rule, they can be carried out at room temperature.To shorten the reaction time, or else to start the reaction, the mixturemay be heated briefly to the boiling point of the reaction mixture. Thereaction times can also be shortened by adding a few drops of base asreaction catalyst. Suitable bases are, in particular, tertiary aminessuch as trimethylamine, triethylamine, quinuclidine,1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or1,5-diazabicyclo-[5.4.0]undec-7-ene. However, inorganic bases such ashydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g.sodium hydroxide or potassium hydroxide, carbonates such as sodiumcarbonate and potassium carbonate, or hydrogen carbonates such aspotassium hydrogen carbonate and sodium hydrogen carbonate may also beused as bases. The bases can be used as such or else with catalyticamounts of a phase-transfer catalyst, for example a crown ether, inparticular 18-crown-6, or a tetraalkylammonium salt.

The compounds of formula I can be isolated in the customary manner byconcentrating and/or by evaporating the solvent and purified byrecrystallization or trituration of the solid residue in solvents inwhich they are not readily soluble, such as ethers, aromatichydrocarbons or chlorinated hydrocarbons.

The compounds I and, where appropriate, the tautomers thereof, can bepresent in the form of one of the isomers which are possible or as amixture of these, for example in the form of pure isomers, such asantipodes and/or diastereomers, or as isomer mixtures, such asenantiomer mixtures, for example racemates, diastereomer mixtures orracemate mixtures, depending on the number, absolute and relativeconfiguration of asymmetric carbon atoms which occur in the moleculeand/or depending on the configuration of non-aromatic double bonds whichoccur in the molecule; the invention relates to the pure isomers andalso to all isomer mixtures which are possible and is to be understoodin each case in this sense hereinabove and hereinbelow, even whenstereochemical details are not mentioned specifically in each case.

The compounds I and, where appropriate, the tautomers thereof, can, ifappropriate, also be obtained in the form of hydrates and/or includeother solvents, for example those which may have been used for thecrystallization of compounds which are present in solid form.

It has now been found that the compounds of formula I according to theinvention have, for practical purposes, a very advantageous spectrum ofactivities for protecting useful plants against diseases that are causedby phytopathogenic microorganisms, such as fungi, bacteria or viruses.

The invention relates to a method of controlling or preventinginfestation of useful plants by phytopathogenic microorganisms, whereina compound of formula I is applied as active ingredient to the plants,to parts thereof or the locus thereof. The compounds of formula Iaccording to the invention are distinguished by excellent activity atlow rates of application, by being well tolerated by plants and by beingenvironmentally safe. They have very useful curative, preventive andsystemic properties and are used for protecting numerous useful plants.The compounds of formula I can be used to inhibit or destroy thediseases that occur on plants or parts of plants (fruit, blossoms,leaves, stems, tubers, roots) of different crops of useful plants, whileat the same time protecting also those parts of the plants that growlater e.g. from phytopathogenic microorganisms.

It is also possible to use compounds of formula I as dressing agents forthe treatment of plant propagation material, in particular of seeds(fruit, tubers, grains) and plant cuttings (e.g. rice), for theprotection against fungal infections as well as against phytopathogenicfungi occurring in the soil.

Furthermore the compounds of formula I according to the invention may beused for controlling fungi in related areas, for example in theprotection of technical materials, including wood and wood relatedtechnical products, in food storage or in hygiene management.

The compounds of formula I are, for example, effective against thephytopathogenic fungi of the following classes: Fungi imperfecti (e.g.Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercosporaand Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia,Puccinia). Additionally, they are also effective against the Ascomycetesclasses (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula)and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara).Outstanding activity has been observed against powdery mildew (Erysiphespp.). Furthermore, the novel compounds of formula I are effectiveagainst phytopathogenic bacteria and viruses (e.g. against Xanthomonasspp, Pseudomonas spp, Erwinia amylovora as well as against the tobaccomosaic virus). Good activity has been observed against Asian soybeanrust (Phakopsora pachyrhizi).

Within the scope of the invention, useful plants to be protectedtypically comprise the following species of plants: cereal (wheat,barley, rye, oat, rice, maize, sorghum and related species); beet (sugarbeet and fodder beet); pomes, drupes and soft fruit (apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries andblackberries); leguminous plants (beans, lentils, peas, soybeans); oilplants (rape, mustard, poppy, olives, sunflowers, coconut, castor oilplants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers,melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges,lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae(avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee,eggplants, sugar cane, tea, pepper, vines, hops, bananas and naturalrubber plants, as well as ornamentals.

The term “useful plants” is to be understood as including also usefulplants that have been rendered tolerant to herbicides like bromoxynil orclasses of herbicides (such as, for example, HPPD inhibitors, ALSinhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron,EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase)inhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant toimidazolinones, e.g. imazamox, by conventional methods of breeding(mutagenesis) is Clearfield® summer rape (Canola). Examples of cropsthat have been rendered tolerant to herbicides or classes of herbicidesby genetic engineering methods include glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady®, Herculex I® and LibertyLink®.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising one or more selectivelyacting toxins, such as are known, for example, from toxin-producingbacteria, especially those of the genus Bacillus.

The term “useful plants” is to be understood as including also usefulplants which have been so transformed by the use of recombinant DNAtechniques that they are capable of synthesising antipathogenicsubstances having a selective action, such as, for example, theso-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392225). Examples of such antipathogenic substances and transgenic plantscapable of synthesising such antipathogenic substances are known, forexample, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. Themethods of producing such transgenic plants are generally known to theperson skilled in the art and are described, for example, in thepublications mentioned above.

The term “locus” of a useful plant as used herein is intended to embracethe place on which the useful plants are growing, where the plantpropagation materials of the useful plants are sown or where the plantpropagation materials of the useful plants will be placed into the soil.An example for such a locus is a field, on which crop plants aregrowing.

The term “plant propagation material” is understood to denote generativeparts of the plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

The compounds of formula I can be used in unmodified form or,preferably, together with carriers and adjuvants conventionally employedin the art of formulation.

Therefore the invention also relates to compositions for controlling andprotecting against phytopathogenic microorganisms, comprising a compoundof formula I and an inert carrier, and to a method of controlling orpreventing infestation of useful plants by phytopathogenicmicroorganisms, wherein a composition, comprising a compound of formulaI as active ingredient and an inert carrier, is applied to the plants,to parts thereof or the locus thereof.

To this end compounds of formula I and inert carriers are convenientlyformulated in known manner to emulsifiable concentrates, coatablepastes, directly sprayable or dilutable solutions, dilute emulsions,wettable powders, soluble powders, dusts, granulates, and alsoencapsulations e.g. in polymeric substances. As with the type of thecompositions, the methods of application, such as spraying, atomising,dusting, scattering, coating or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances. Thecompositions may also contain further adjuvants such as stabilizers,antifoams, viscosity regulators, binders or tackifiers as well asfertilizers, micronutrient donors or other formulations for obtainingspecial effects.

Suitable carriers and adjuvants can be solid or liquid and aresubstances useful in formulation technology, e.g. natural or regeneratedmineral substances, solvents, dispersants, wetting agents, tackifiers,thickeners, binders or fertilizers. Such carriers are for exampledescribed in WO 97/33890.

The compounds of formula I or compositions, comprising a compound offormula I as active ingredient and an inert carrier, can be applied tothe locus of the plant or plant to be treated, simultaneously or insuccession with further compounds. These further compounds can be e.g.fertilizers or micronutrient donors or other preparations whichinfluence the growth of plants. They can also be selective herbicides aswell as insecticides, fungicides, bactericides, nematicides,molluscicides or mixtures of several of these preparations, if desiredtogether with further carriers, surfactants or application promotingadjuvants customarily employed in the art of formulation.

A preferred method of applying a compound of formula I, or acomposition, comprising a compound of formula I as active ingredient andan inert carrier, is foliar application. The frequency of applicationand the rate of application will depend on the risk of infestation bythe corresponding pathogen. However, the compounds of formula I can alsopenetrate the plant through the roots via the soil (systemic action) bydrenching the locus of the plant with a liquid formulation, or byapplying the compounds in solid form to the soil, e.g. in granular form(soil application). In crops of water rice such granulates can beapplied to the flooded rice field. The compounds of formula I may alsobe applied to seeds (coating) by impregnating the seeds or tubers eitherwith a liquid formulation of the fungicide or coating them with a solidformulation.

A formulation, i.e. a composition comprising the compound of formula Iand, if desired, a solid or liquid adjuvant, is prepared in a knownmanner, typically by intimately mixing and/or grinding the compound withextenders, for example solvents, solid carriers and, optionally,surface-active compounds (surfactants).

The agrochemical formulations will usually contain from 0.1 to 99% byweight, preferably from 0.1 to 95% by weight, of the compound of formulaI, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid orliquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25%by weight, of a surfactant.

Whereas it is preferred to formulate commercial products asconcentrates, the end user will normally use dilute formulations.

Advantageous rates of application are normally from 5 g to 2 kg ofactive ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kga.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as seeddrenching agent, convenient rates of application are from 10 mg to 1 gof active substance per kg of seeds. The rate of application for thedesired action can be determined by experiments. It depends for exampleon the type of action, the developmental stage of the useful plant, andon the application (location, timing, application method) and can, owingto these parameters, vary within wide limits.

Surprisingly, it has now been found that the compounds of formula I canalso be used in methods of protecting crops of useful plants againstattack by phytopathogenic organisms as well as the treatment of crops ofuseful plants infested by phytopathogenic organisms comprisingadministering a combination of glyphosate and at least one compound offormula I to the plant or locus thereof, wherein the plant is resistantor sensitive to glyphosate.

Said methods may provide unexpectedly improved control of diseasescompared to using the compounds of formula I in the absence ofglyphosate. Said methods may be effective at enhancing the control ofdisease by compounds of formula I. While the mixture of glyphosate andat least one compound of formula I may increase the disease spectrumcontrolled, at least in part, by the compound of formula I, an increasein the activity of the compound of formula I on disease species alreadyknown to be controlled to some degree by the compound of formula I canalso be the effect observed.

Said methods are particularly effective against the phytopathogenicorganisms of the kingdom Fungi, phylum Basidiomycot, classUredinomycetes, subclass Urediniomycetidae and the order Uredinales(commonly referred to as rusts). Species of rusts having a particularlylarge impact on agriculture include those of the family Phakopsoraceae,particularly those of the genus Phakopsora, for example Phakopsorapachyrhizi, which is also referred to as Asian soybean rust, and thoseof the family Pucciniaceae, particularly those of the genus Pucciniasuch as Puccinia graminis, also known as stem rust or black rust, whichis a problem disease in cereal crops and Puccinia recondita, also knownas brown rust.

An embodiment of said method is a method of protecting crops of usefulplants against attack by a phytopathogenic organism and/or the treatmentof crops of useful plants infested by a phytopathogenic organism, saidmethod comprising simultaneously applying glyphosate, including salts oresters thereof, and at least one compound of formula I, which hasactivity against the phytopathogenic organism to at least one memberselected from the group consisting of the plant, a part of the plant andthe locus of the plant.

The compounds of formula (I), or a pharmaceutical salt thereof,described above may also an advantageous spectrum of activity for thetreatment and/or prevention of microbial infection in an animal.

“Animal” can be any animal, for example, insect, mammal, reptile, fish,amphibian, preferably mammal, most preferably human. “Treatment” meansthe use on an animal which has microbial infection in order to reduce orslow or stop the increase or spread of the infection, or to reduce theinfection or to cure the infection. “Prevention” means the use on ananimal which has no apparent signs of microbial infection in order toprevent any future infection, or to reduce or slow the increase orspread of any future infection.

According to the present invention there is provided the use of acompound of formula (I) in the manufacture of a medicament for use inthe treatment and/or prevention of microbial infection in an animal.There is also provided the use of a compound of formula (I) as apharmaceutical agent. There is also provided the use of a compound offormula (I) as an antimicrobial agent in the treatment of an animal.According to the present invention there is also provided apharmaceutical composition comprising as an active ingredient a compoundof formula (I), or a pharmaceutically acceptable salt thereof, and apharmaceutically acceptable diluent or carrier. This composition can beused for the treatment and/or prevention of antimicrobial infection inan animal. This pharmaceutical composition can be in a form suitable fororal administration, such as tablet, lozenges, hard capsules, aqueoussuspensions, oily suspensions, emulsions dispersible powders,dispersible granules, syrups and elixirs. Alternatively thispharmaceutical composition can be in a form suitable for topicalapplication, such as a spray, a cream or lotion. Alternatively thispharmaceutical composition can be in a form suitable for parenteraladministration, for example injection. Alternatively this pharmaceuticalcomposition can be in inhalable form, such as an aerosol spray.

The compounds of formula (I) may be effective against various microbialspecies able to cause a microbial infection in an animal. Examples ofsuch microbial species are those causing Aspergillosis such asAspergillus fumigatus, A. flavus, A. terrus, A. nidulans and A. niger,those causing Blastomycosis such as Blastomyces dermatitidis; thosecausing Candidiasis such as Candida albicans, C. glabrata, C.tropicalis, C. parapsilosis, C. krusei and C. lusitaniae; those causingCoccidioidomycosis such as Coccidioides immitis; those causingCryptococcosis such as Cryptococcus neoformans; those causingHistoplasmosis such as Histoplasma capsulatum and those causingZygomycosis such as Absidia colymbifera, Rhizomucor pusillus andRhizopus arrhizus. Further examples are Fusarium Spp such as Fusariumoxysporum and Fusarium solani and Scedosporium Spp such as Scedosporiumapiospermum and Scedosporium prolificans. Still further examples areMicrosporum Spp, Trichophyton Spp, Epidermophyton Spp, Mucor Spp,Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp,Paracoccidioides Spp and Histoplasma Spp.

The following non-limiting Examples illustrate the above-describedinvention in greater detail without limiting it.

PREPARATION EXAMPLES Example P1 Preparation of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid[2-(3-chloro-5-cyclopropylethinylthiophen-2-yl)-1-methylethyl]amide(Compound 1.26)

In a sulfonation flask a mixture containing of 240 mg (0.58 mmol)3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid[2-(5-bromo-3-chlorothiophen-2-yl)-1-methylethyl]amide, 80 mg (1.15mmol) cyclopropyacetylene, 10 mg copper(I)iodide, 36 mg (0.05 mmol)bistriphenylphosphine palladium dichloride and 30 ml triethylamine isstirred at 60° C. for 2 days. Then another 80 mg of cyclopropylacetyleneis added and stirring continued for 24 hours. After cooling to ambienttemperature ethylacetate and water is added and the organic layerseparated and washed again twice with water. After drying (sodiumsulphate) and distilling off the solvent in a water jet vacuum, thecrude product is obtained. Purification is achieved by columnchromatography over silicagel (eluent: ethylacetate/heptane 1:1). Yield:90 mg (23% of theory) of a slightly brown resin (¹H-NMR: 0.8/m/2H,0.9/m/2H, 1.22/d/3H, 1.45/m/1H, 3.01/d/2H, 3.9/s/3H, 4.40/m/1H, 6.28/s(broad)/1H, 6.88/t/1H—CF₂H, 6.89/s/1H, 7.85/s/1H).

Example P2 Preparation of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid{2-[3-chloro-5-(4-fluorophenyl)thiophen-2-yl]-1-methylethyl}amide(Compound 1.46)

In a sulfonation flask a mixture containing of 207 mg (0.5 mmol)3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid[2-(5-bromo-3-chlorothiophen-2-yl)-1-methylethyl]amide, 90 mg (0.64mmol) 4-fluorophenylboronic acid, 151 mg (1.8 mmol) sodiumbicarbonate,36 mg (0.05 mmol) bistriphenylphosphine palladium dichloride, 10 mldimethoxyethane and 5 ml of water is stirred at reflux for 6 hours.After cooling to ambient temperature ethylacetate and water is added andthe organic layer separated and washed again twice with water. Afterdrying (sodium sulphate) and distilling off the solvent in a water jetvacuum, the crude product is obtained. Purification is achieved bycolumn chroma-tography over silicagel (eluent: ethylacetate/heptane1:1). Yield: 180 mg (80% of theory) of a slightly brown oil (1H-NMR:1.29/d/3H, 0.9/m/2H, 3.09/m/2H, 3.89/s/3H, 4.42/m/1H, 6.38/s (broad)/1H,6.89/t/1H—CF₂H, 7.05/m/2H, 7.48/m/2H, 7.89/s/1H).

Example P3 Preparation of1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid{2-[2,4-dichloro-5-(4-fluorophenyl)-thiophen-3-yl]-1-methylethyl}amide(Compound 7.70) and 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylicacid {2-[4,5-dichloro-2-(4-fluorophenyl)-thiophen3-yl]1-methylethyl}amide (Compound 7.72)

In a sulfonation flask 280 mg (0.6 mmol) of the isomeric amide mixtureobtained in example P5c) is dissolved in 10 ml of 1,2-dimethoxyethane.After addition of 105 mg (0.75 mmol) 4-fluorophenylboronic acid, 35 mg(0.05 mmol) bis(triphenylphosphine)palladium dichloride and 225 mg (2.7mmol) sodium bicarbonate dissolved in 5 ml water, the resulting mixtureis stirred for 3 hours at 70-75° C. After cooling 100 ml of water isadded and the mixture extracted 3 times with ethylacetate. The organiclayer is washed with brine and after drying (sodium sulphate) andevaporation of the solvent the crude isomer mixture is obtained. A firstpurification is achieved by column chromatography over silicagel(eluent: ethylacetate/heptane 1:1). The isolation of the twofluoro-phenyl-isomers is achieved by HPLC (high pressure liquidchromatography). Regioisomer I (compound 7.70) is obtained in pure formas a colourless oil (¹H-NMR: 1.31/d/3H, 2.9/m/2H(diastereotopicprotons), 3.97/s/3H, 4.55/m/1H, 5.98/d (broad)/1H, 7.12/t/2H, 7.53/m/2H,7.87/s/1H). Regioisomer 2 (compound 7.72) could also be obtained in pureform (84 mg=29% of theory) in the form of white crystals (m.p.: 127-130°C.).

Example P4 Preparation of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid[2-(5-bromo-3-chlorothiophen-2-yl)-1-methylethyl]amide (CompoundZ1.2) a) Preparation of 3-chloro-2-((E)-nitropropenyl)thiophene

In a sulfonation flask, a mixture containing 11.7 g (0.08 mol)3-chlorothiophene-2-carbaldehyde, 48 g (0.64 mol) nitroethane, 15.4 g(0.2 mol) ammoniumacetate and 160 ml acetic acid is heated at 90° C. for5 hours. After cooling ethylacetate is added and the organic phasewashed three times with water. The organic phase is dried over sodiumsulphate and after filtration the organic solvent is distilled off in awater jet vacuum. The residue is purified by column chromatography oversilicagel (eluent: ethylacetate/heptane 1:5). Yield: 10.8 g (67% oftheory) of a colourless oil (¹H-NMR: 2.57/s/3H, 7.12/d/1H, 7.62/d/1H,8.45/s/1H).

b) Preparation of 2-(3-chlorothiophen-2-yl)-1-methylethylamine

In a sulfonation flask 5.4 g (0.0265 mol)3-chloro-2-((E)-nitropropenyl)thiophene is added to 120 ml a 1 molaretheral solution of LiAlH₄ (0.12 mol) in such a manner that the internaltemperature remains constant at 0-5° C. The mixture is then stirred for4 hours at 20° C. After quenching at 5° C. with the minimum amount ofwater, sodium sulphate is added. After filtration and distilling off thesolvent in a water jet vacuum a solution, the crude material isobtained. Purification is achieved by column chromatography oversilicagel (eluent: tert. butylmethylether/EtOH 3:1). Yield: 34.6 g (74%of theoery) of a colourless oil (¹H-NMR: 1.18/d/3H, 1.42/s/NH₂,2.72-2.9/m (diasterotopic protons)/2H, 3.25/m/1H, 6.89/d/1H, 7.16/d/1H).

c) Preparation of 2-(5-bromo-3-chlorothiophen-2-yl)-1-methylethylamine(compound Z2.2)

In a sulfonation flask 5 g (0.028 mol)2-(3-chlorothiphen-2-yl)-1-methylethylamine is dissolved in 70 ml ofacetic acid. The mixture is then cooled to 15° C. and 4.8 g (0.30 m) ofbromine is added under stirring (internal temperature 15-17° C.). Afterwarming up to rt, the mixture is stirred for 16 hours. Then the mixtureis poured to a mixture of tert. butylmethylether (ca. 250 ml) and 2Nsodiumhydroxide. The final pH is 11. After washing with brine, dryingwith sodium sulphate and evaporation of the solvent the crude materialis obtained. Purification is achieved by column chromatography oversilicagel (eluent: tert. butylmethylether/EtOH 10:1). Yield: 5.4 g (75%of theory) of a colourless oil (¹H-NMR: 1.18/d/3H, 2.68-2.87/m(diasterotopic protons)/2H, 3.2/m/1H, 6.87/s/1H).

d) Preparation of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid[2-(5-bromo-3-chlorothiophen-2-yl)-1-methylethyl]amide (compoundZ1.2)

In a sulfonation flask 1 g (4 mmol) of the amine prepared in example 3and 1 ml (6 mmol) triethylamine are dissolved in 30 ml ofmethylenechloride. Then a mixture of 780 mg (4 mmol)3-difluoromethyl-1-methyl-1-H-pyrazole 4-carboxylic acid chloride and 10ml methylenechloride is added at room temperature under stirring. Afterstirring for 16 hours the solvent is evaporated in a water jet vacuumand the residue purified by column chromatography over silicagel(eluent: ethylacetate/hexane 1:1). Yield: 1.65 g (83% of theory) ofwhite crystals. M.p. 157-158° C.

Example P5 Preparation of3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylicacid[2-(5-bromo-3-chlorothiophen-2-yl)-1-methylethyl]amide (CompoundZ1.2) a) Preparation of 2-(4,5-dichlorothiophen-3-yl)-1-methylethylamineand 2-(2,4-dichlorothiophen-3-yl)-1-methylethylamine

In a sulfonation flask 10 ml (10 mmol) of a 1 molar ethereal LiAlH₄solution is slowly added to 30 ml of tetrahydrofurane. Then a solutionof 0.9 g (3.32 mmol) 2,3,5-trichloro-4-((E)-2-nitropropenyl)thiophene isadded slowly in such a manner that the internal temperature remainsconstant between 10-12° C. Stirring continued for 3 hours at 10-12° C.Then the mixture is quenched with 0.4 ml of water and 0.38 gsodiumhydroxide solution (15%). After addition of 5 ml saturatedammoniumchloride solution the suspension is filtered. The liquid layeris dried and then the solvent is distilled off in a water jet vacuum.The raw material is purified by column chromatography over silicagel(eluent: tert.butylmethylether/ethanol 20:1—1:1). The obtained mixtureof amines (0.4 g) contains 27% of2-(4,5-dichlorothiophen-3-yl)-1-methylethylamine, 30% of2-(2,4-dichlorothiophen-3-yl)-1-methylethylamine and 43% of theundesired trichloro-compound2-(2,4,5-trichlorothiophen-3-yl)-1-methylethylamine.

b) Preparation of2-(2-bromo-4,5-dichlorothiophen-3-yl)-1-methyl-ethylamine and2-(5-bromo-2,4-dichlorothiophen-3-yl)-1-methylethylamine

In a sulfonation flask 2.49 g (11.9 mmol) of the isomer mix obtained inexample P5a) is dissolved in 25 ml of acetic acid. Then 1.99 g (12.4mmol) of bromine is added dropwise during 5 minutes. Stirring continuedfor 16 hours at room temperature and then the acid is evaporated in awater jet vacuum. The solid residue was poured into 50 ml of saturatedsodiumhydrocarbonate solution and then the water phase is extracted 3times with ter.butylmethylether. After drying (sodium sulphate) anddistilling off the solvent in a water jet vacuum the crude material isobtained. Purification is achieved by column chromatography oversilicagel (eluent: tert.butylmethylether/ethanol 20:1-1:1). 2.1 g of abrown oil consisting of an isomer mixture of 27%2-(2-bromo-4,5-dichlorothiophen-3-yl)-1-methyl-ethylamine, 27%2-(5-bromo-2,4-dichlorothiophen-3-yl)-1-methylethylamine and 43% of theundesired 2-(2,4,5-trichlorothiophen-3-yl)-1-methylethylamine.

c) Preparation of 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylicacid [2-(2-bromo-4,5-dichlorothiophen-3-yl)-1-methylethyl]amide and1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid[2-(5-bromo-2,4-dichlorothiophen-3-yl)-1-methylethyl]amide

In a sulfonation flask 2.07 g (7.2 mmol) of the amine isomer mixtureprepared in example P5b) and 1.45 g (14.4 mmol) triethylamine aredissolved in 50 ml of methylenechloride. Then a mixture of 1.65 g (7.2mmol) 3-trifluoromethyl-1-methyl-1-H-pyrazole 4-carboxylic acid chlorideand 50 ml methylenechloride is added at room temperature under stirring.After stirring for 16 hours the solvent is evaporated in a water jetvacuum and the residue purified by column chromatography over silicagel(eluent: ethylacetate/heptane 1:2-2:1). 1.52 g of an isomeric mixture ofamides is obtained in the form of slightly brown crystals (m.p.:134-138° C.). The mixture consists of 27% of1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid[2-(2-bromo-4,5-dichlorothiophen-3-yl)-1-methylethyl]amide, 30% of1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid[2-(5-bromo-2,4-dichlorothiophen-3-yl)-1-methylethyl]amide and 43% ofthe undesired 1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid[2-(2,4,5-trichlorothiophen-3-yl)-1-methylethyl]amide.

Tables 1 to 14: Compounds of Formula I

The invention is further illustrated by the preferred individualcompounds of formula (I) listed below in Tables 1 to 14. Characterisingdata is given in Table 21.

TABLE 1 Compounds of formula Ia (Ia)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ R₈ 1.1 H Cl

H Me Me F 1.2 Me Cl

H Me Me F 1.3 H Br

H Me Me F 1.4 Me Br

H Me Me F 1.5 H Cl

H Me Me F 1.6 Me Cl

H Me Me F 1.7 H Br

H Me Me F 1.8 Me Br

H Me Me F 1.9 H Cl

H Me Me F 1.10 Me Cl

H Me Me F 1.11 H Br

H Me Me F 1.12 Me Br

H Me Me F 1.13 H Cl

H Me Me F 1.14 Me Cl

H Me Me F 1.15 H Br

H Me Me F 1.16 Me Br

H Me Me F 1.17 H Cl

H Me Me F 1.18 Me Cl

H Me Me F 1.19 H Br

H Me Me F 1.20 Me Br

H Me Me F 1.21 H Cl

H Me Me F 1.22 Me Cl

H Me Me F 1.23 H Br

H Me Me F 1.24 Me Br

H Me Me F 1.25 H Cl

H CF₂H Me H 1.26 Me Cl

H CF₂H Me H 1.27 H Br

H CF₂H Me H 1.28 Me Br

H CF₂H Me H 1.29 H Cl

H CF₂H Me H 1.30 Me Cl

H CF₂H Me H 1.31 H Br

H CF₂H Me H 1.32 Me Br

H CF₂H Me H 1.33 H Cl

H CF₂H Me H 1.34 Me Cl

H CF₂H Me H 1.35 H Br

H CF₂H Me H 1.36 Me Br

H CF₂H Me H 1.37 H Cl

H CF₂H Me H 1.38 Me Cl

H CF₂H Me H 1.39 H Br

H CF₂H Me H 1.40 Me Br

H CF₂H Me H 1.41 H Cl

H CF₂H Me H 1.42 Me Cl

H CF₂H Me H 1.43 H Br

H CF₂H Me H 1.44 Me Br

H CF₂H Me H 1.45 H Cl

H CF₂H Me H 1.46 Me Cl

H CF₂H Me H 1.47 H Br

H CF₂H Me H 1.48 Me Br

H CF₂H Me H 1.49 H Cl

H CF₃ Me H 1.50 Me Cl

H CF₃ Me H 1.51 H Br

H CF₃ Me H 1.52 Me Br

H CF₃ Me H 1.53 H Cl

H CF₃ Me H 1.54 Me Cl

H CF₃ Me H 1.55 H Br

H CF₃ Me H 1.56 Me Br

H CF₃ Me H 1.57 H Cl

H CF₃ Me H 1.58 Me Cl

H CF₃ Me H 1.59 H Br

H CF₃ Me H 1.60 Me Br

H CF₃ Me H 1.61 H Cl

H CF₃ Me H 1.62 Me Cl

H CF₃ Me H 1.63 H Br

H CF₃ Me H 1.64 Me Br

H CF₃ Me H 1.65 H Cl

H CF₃ Me H 1.66 Me Cl

H CF₃ Me H 1.67 H Br

H CF₃ Me H 1.68 Me Br

H CF₃ Me H 1.69 H Cl

H CF₃ Me H 1.70 Me Cl

H CF₃ Me H 1.71 H Br

H CF₃ Me H 1.72 Me Br

H CF₃ Me H

TABLE 2 Compound of formula Ib (Ib)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 2.1 H Cl

H CF₂H Me 2.2 Me Cl

H CF₂H Me 2.3 H Br

H CF₂H Me 2.4 Me Br

H CF₂H Me 2.5 H Cl

H CF₂H Me 2.6 Me Cl

H CF₂H Me 2.7 H Br

H CF₂H Me 2.8 Me Cl

H CF₂H Me 2.9 H Cl

H CF₂H Me 2.10 Me Cl

H CF₂H Me 2.11 H Br

H CF₂H Me 2.12 Me Br

H CF₂H Me 2.13 H Cl

H CF₂H Me 2.14 Me Cl

H CF₂H Me 2.15 H Br

H CF₂H Me 2.16 Me Br

H CF₂H Me 2.17 H Cl

H CF₂H Me 2.18 Me Cl

H CF₂H Me 2.19 H Br

H CF₂H Me 2.20 Me Br

H CF₂H Me 2.21 H Cl

H CF₂H Me 2.22 Me Cl

H CF₂H Me 2.23 H Br

H CF₂H Me 2.24 Me Br

H CF₂H Me 2.25 H Cl

H CF₃ Me 2.26 Me Cl

H CF₃ Me 2.27 H Br

H CF₃ Me 2.28 Me Br

H CF₃ Me 2.29 H Cl

H CF₃ Me 2.30 Me Cl

H CF₃ Me 2.31 H Br

H CF₃ Me 2.32 Me Cl

H CF₃ Me 2.33 H Cl

H CF₃ Me 2.34 Me Cl

H CF₃ Me 2.35 H Br

H CF₃ Me 2.36 Me Br

H CF₃ Me 2.37 H Cl

H CF₃ Me 2.38 Me Cl

H CF₃ Me 2.39 H Br

H CF₃ Me 2.40 Me Br

H CF₃ Me 2.41 H Cl

H CF₃ Me 2.42 Me Cl

H CF₃ Me 2.43 H Br

H CF₃ Me 2.44 Me Br

H CF₃ Me 2.45 H Cl

H CF₃ Me 2.46 Me Cl

H CF₃ Me 2.47 H Br

H CF₃ Me 2.48 Me Br

H CF₃ Me

TABLE 3 Compounds of Formula Ic (Ic)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 3.1 H Cl

H CF₂H Me 3.2 Me Cl

H CF₂H Me 3.3 H Br

H CF₂H Me 3.4 Me Br

H CF₂H Me 3.5 H Cl

H CF₂H Me 3.6 Me Cl

H CF₂H Me 3.7 H Br

H CF₂H Me 3.8 Me Cl

H CF₂H Me 3.9 H Cl

H CF₂H Me 3.10 Me Cl

H CF₂H Me 3.11 H Br

H CF₂H Me 3.12 Me Br

H CF₂H Me 3.13 H Cl

H CF₂H Me 3.14 Me Cl

H CF₂H Me 3.15 H Br

H CF₂H Me 3.16 Me Br

H CF₂H Me 3.17 H Cl

H CF₂H Me 3.18 Me Cl

H CF₂H Me 3.19 H Br

H CF₂H Me 3.20 Me Br

H CF₂H Me 3.21 H Cl

H CF₂H Me 3.22 Me Cl

H CF₂H Me 3.23 H Br

H CF₂H Me 3.24 Me Br

H CF₂H Me 3.25 H Cl

H CF₃ Me 3.26 Me Cl

H CF₃ Me 3.27 H Br

H CF₃ Me 3.28 Me Br

H CF₃ Me 3.29 H Cl

H CF₃ Me 3.30 Me Cl

H CF₃ Me 3.31 H Br

H CF₃ Me 3.32 Me Cl

H CF₃ Me 3.33 H Cl

H CF₃ Me 3.34 Me Cl

H CF₃ Me 3.35 H Br

H CF₃ Me 3.36 Me Br

H CF₃ Me 3.37 H Cl

H CF₃ Me 3.38 Me Cl

H CF₃ Me 3.39 H Br

H CF₃ Me 3.40 Me Br

H CF₃ Me 3.41 H Cl

H CF₃ Me 3.42 Me Cl

H CF₃ Me 3.43 H Br

H CF₃ Me 3.44 Me Br

H CF₃ Me 3.45 H Cl

H CF₃ Me 3.46 Me Cl

H CF₃ Me 3.47 H Br

H CF₃ Me 3.48 Me Br

H CF₃ Me

TABLE 4 Compounds of formula Id (Id)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 4.1 H Cl

H CF₂H Me 4.2 Me Cl

H CF₂H Me 4.3 H Br

H CF₂H Me 4.4 Me Br

H CF₂H Me 4.5 H Cl

H CF₂H Me 4.6 Me Cl

H CF₂H Me 4.7 H Br

H CF₂H Me 4.8 Me Cl

H CF₂H Me 4.9 H Cl

H CF₂H Me 4.10 Me Cl

H CF₂H Me 4.11 H Br

H CF₂H Me 4.12 Me Br

H CF₂H Me 4.13 H Cl

H CF₂H Me 4.14 Me Cl

H CF₂H Me 4.15 H Br

H CF₂H Me 4.16 Me Br

H CF₂H Me 4.17 H Cl

H CF₂H Me 4.18 Me Cl

H CF₂H Me 4.19 H Br

H CF₂H Me 4.20 Me Br

H CF₂H Me 4.21 Me Cl

H CF₂H Me 4.22 Me Cl

H CF₂H Me 4.23 H Br

H CF₂H Me 4.24 Me Br

H CF₂H Me 4.25 H Cl

H CF₃ Me 4.26 Me Cl

H CF₃ Me 4.27 H Br

H CF₃ Me 4.28 Me Br

H CF₃ Me 4.29 H Cl

H CF₃ Me 4.30 Me Cl

H CF₃ Me 4.31 H Br

H CF₃ Me 4.32 Me Cl

H CF₃ Me 4.33 H Cl

H CF₃ Me 4.34 Me Cl

H CF₃ Me 4.35 H Br

H CF₃ Me 4.36 Me Br

H CF₃ Me 4.37 H Cl

H CF₃ Me 4.38 Me Cl

H CF₃ Me 4.39 H Br

H CF₃ Me 4.40 Me Br

H CF₃ Me 4.41 H Cl

H CF₃ Me 4.42 Me Cl

H CF₃ Me 4.43 H Br

H CF₃ Me 4.44 Me Br

H CF₃ Me 4.45 H Cl

H CF₃ Me 4.46 Me Cl

H CF₃ Me 4.47 H Br

H CF₃ Me 4.48 Me Br

H CF₃ Me

Compounds of formula Ie (Ie)

Compound Number R₁ R₃ R₄ R₅ R₆ 5.1 H Cl

H Cl 5.2 Me Cl

H Cl 5.3 H Cl

H Br 5.4 Me Cl

H Br 5.5 H Cl

H CF₃ 5.6 Me Cl

H CF₃ 5.7 H Br

H Cl 5.8 Me Br

H Cl 5.9 H Br

H Br 5.10 Me Br

H Br 5.11 H Br

H CF₃ 5.12 Me Br

H CF₃ 5.13 H Cl

H Cl 5.14 Me Cl

H Cl 5.15 H Cl

H Br 5.16 Me Cl

H Br 5.17 H Cl

H CF₃ 5.18 Me Cl

H CF₃ 5.19 H Br

H Cl 5.20 Me Br

H Cl 5.21 H Br

H Br 5.22 Me Br

H Br 5.23 H Br

H CF₃ 5.24 Me Br

H CF₃ 5.25 H Cl

H Cl 5.26 Me Cl

H Cl 5.27 H Cl

H Br 5.28 Me Cl

H Br 5.29 H Cl

H CF₃ 5.30 Me Cl

H CF₃ 5.31 H Br

H Cl 5.32 Me Br

H Cl 5.33 H Br

H Br 5.34 Me Br

H Br 5.35 H Br

H CF₃ 5.36 Me Br

H CF₃ 5.37 H Cl

H Cl 5.38 Me Cl

H Cl 5.39 H Cl

H Br 5.40 Me Cl

H Br 5.41 H Cl

H CF₃ 5.42 Me Cl

H CF₃ 5.43 H Br

H Cl 5.44 Me Br

H Cl 5.45 H Br

H Br 5.46 Me Br

H Br 5.47 H Br

H CF₃ 5.48 Me Br

H CF₃ 5.49 H Cl

H Cl 5.50 Me Cl

H Cl 5.51 H Cl

H Br 5.52 Me Cl

H Br 5.53 H Cl

H CF₃ 5.54 Me Cl

H CF₃ 5.55 H Br

H Cl 5.56 Me Br

H Cl 5.57 H Br

H Br 5.58 Me Br

H Br 5.59 H Br

H CF₃ 5.60 Me Br

H CF₃ 5.61 H Cl

H Cl 5.62 Me Cl

H Cl 5.63 H Cl

H Br 5.64 Me Cl

H Br 5.65 H Cl

H CF₃ 5.66 Me Cl

H CF₃ 5.67 H Br

H Cl 5.68 Me Br

H Cl 5.69 H Br

H Br 5.70 Me Br

H Br 5.71 H Br

H CF₃ 5.72 Me Br

H CF₃

TABLE 6 Compounds of formula If (If)

Compound Number R₁ R₃ R₄ R₅ R₆ 6.1 H Cl

H CF₂H 6.2 Me Cl

H CF₃ 6.3 H Br

H CF₂H 6.4 Me Br

H CF₃ 6.5 H Cl

H CF₂H 6.6 Me Cl

H CF₃ 6.7 H Br

H CF₂H 6.8 Me Br

H CF₃ 6.9 H Cl

H CF₂H 6.10 Me Cl

H CF₃ 6.11 H Br

H CF₂H 6.12 Me Br

H CF₃ 6.13 H Cl

H CF₂H 6.14 Me Cl

H CF₃ 6.15 H Br

H CF₂H 6.16 Me Br

H CF₃ 6.17 H Cl

H CF₂H 6.18 Me Cl

H CF₃ 6.19 H Br

H CF₂H 6.20 Me Br

H CF₃ 6.21 H Cl

H CF₂H 6.22 Me Cl

H CF₃ 6.23 H Br

H CF₂H 6.24 Me Br

H CF₃

TABLE 7 Compounds of formula Ig (Ig)

Com- pound Number R₁ R₃ R₄ R₅ R₆ R₇ R₈ 7.1 H 4′-Cl

2′-Cl Me Me F 7.2 Me 4′-Cl

2′-Cl Me Me F 7.3 H 4′-Cl

5′-Cl Me Me F 7.4 Me 4′-Cl

5′-Cl Me Me F 7.5 H 4′-Cl

2′-Cl Me Me F 7.6 Me 4′-Cl

2′-Cl Me Me F 7.7 H 4′-Cl

4′-Cl Me Me F 7.8 Me 4′-Cl

5′-Cl Me Me F 7.9 H 4′-Cl

2′-Cl Me Me F 7.10 Me 4′-Cl

2′-Cl Me Me F 7.11 H 4′-Cl

5′-Cl Me Me F 7.12 Me 4′-Cl

5′-Cl Me Me F 7.13 H 4′-Cl

2′-Cl Me Me F 7.14 Me 4′-Cl

2′-Cl Me Me F 7.15 H 4′-Cl

5′-Cl Me Me F 7.16 Me 4′-Cl

5′-Cl Me Me F 7.17 H 4′-Cl

2′-Cl Me Me F 7.18 Me 4′-Cl

5′-Cl Me Me F 7.19 H 4′-Cl

5′-Cl Me Me F 7.20 Me 4′-Cl

5′-Cl Me Me F 7.21 H 4′-Cl

2′-Cl Me Me F 7.22 Me 4′-Cl

2′-Cl Me Me F 7.23 H 4′-Cl

5′-Cl Me Me F 7.24 Me 4′-Cl

5′-Cl Me Me F 7.25 H 4′-Cl

2′-Cl CF₂H Me H 7.26 Me 4′-Cl

2′-Cl CF₂H Me H 7.27 H 4′-Cl

5′-Cl CF₂H Me H 7.28 Me 4′-Cl

5′-Cl CF₂H Me H 7.29 H 4′-Cl

2′-Cl CF₂H Me H 7.30 Me 4′-Cl

2′-Cl CF₂H Me H 7.31 H 4′-Cl

5′-Cl CF₂H Me H 7.32 Me 4′-Cl

5′-Cl CF₂H Me H 7.33 H 4′-Cl

2′-Cl CF₂H Me H 7.34 Me 4′-Cl

2′-Cl CF₂H Me H 7.35 H 4′-Cl

5′-Cl CF₂H Me H 7.36 Me 4′-Cl

5′-Cl CF₂H Me H 7.37 H 4′-Cl

2′-Cl CF₂H Me H 7.38 Me 4′-Cl

2′-Cl CF₂H Me H 7.39 H 4′-Cl

2′-Cl CF₂H Me H 7.40 Me 4′-Cl

5′-Cl CF₂H Me H 7.41 H 4′-Cl

2′-Cl CF₂H Me H 7.42 Me 4′-Cl

2′-Cl CF₂H Me H 7.43 H 4′-Cl

5′-Cl CF₂H Me H 7.44 Me 4′-Cl

5′-Cl CF₂H Me H 7.45 H 4′-Cl

2′-Cl CF₂H Me H 7.46 Me 4′-Cl

2′-Cl CF₂H Me H 7.47 H 4′-Cl

5′-Cl CF₂H Me H 7.48 Me 4′-Cl

5′-Cl CF₂H Me H 7.49 H 4′-Cl

2′-Cl CF₃ Me H 7.50 Me 4′-Cl

2′-Cl CF₃ Me H 7.51 H 4′-Cl

5′-Cl CF₃ Me H 7.52 Me 4′-Cl

5′-Cl CF₃ Me H 7.53 H 4′-Cl

2′-Cl CF₃ Me H 7.54 Me 4′-Cl

2′-Cl CF₃ Me H 7.55 H 4′-Cl

5′-Cl CF₃ Me H 7.56 Me 4′-Cl

5′-Cl CF₃ Me H 7.57 H 4′-Cl

2′-Cl CF₃ Me H 7.58 Me 4′-Cl

2′-Cl CF₃ Me H 7.59 H 4′-Cl

5′-Cl CF₃ Me H 7.60 Me 4′-Cl

5′-Cl CF₃ Me H 7.61 H 4′-Cl

2′-Cl CF₃ Me H 7.62 Me 4′-Cl

2′-Cl CF₃ Me H 7.63 H 4′-Cl

5′-Cl CF₃ Me H 7.64 Me 4′-Cl

5′-Cl CF₃ Me H 7.65 H 4′-Cl

2′-Cl CF₃ Me H 7.66 Me 4′-Cl

2′-Cl CF₃ Me H 7.67 H 4′-Cl

5′-Cl CF₃ Me H 7.68 Me 4′-Cl

5′-Cl CF₃ Me H 7.69 H 4′-Cl

2′-Cl CF₃ Me H 7.70 Me 4′-Cl

2′-Cl CF₃ Me H 7.71 H 4′-Cl

5′-Cl CF₃ Me H 7.72 Me 4′-Cl

5′-Cl CF₃ Me H

TABLE 8 Compound of formula Ih (Ih)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 8.1 H 4′-Cl

2′-Cl CF₂H Me 8.2 Me 4′-Cl

2′-Cl CF₂H Me 8.3 H 4′-Cl

5′-Cl CF₂H Me 8.4 Me 4′-Cl

5′-Cl CF₂H Me 8.5 H 4′-Cl

2′-Cl CF₂H Me 8.6 Me 4′-Cl

2′-Cl CF₂H Me 8.7 H 4′-Cl

5′-Cl CF₂H Me 8.8 Me 4′-Cl

5′-Cl CF₂H Me 8.9 H 4′-Cl

2′-Cl CF₂H Me 8.10 Me 4′-Cl

2′-Cl CF₂H Me 8.11 H 4′-Cl

5′-Cl CF₂H Me 8.12 Me 4′-Cl

5′-Cl CF₂H Me 8.13 H 4′-Cl

2′-Cl CF₂H Me 8.14 Me 4′-Cl

2′-Cl CF₂H Me 8.15 H 4′-Cl

5′-Cl CF₂H Me 8.16 Me 4′-Cl

5′-Cl CF₂H Me 8.17 H 4′-Cl

2′-Cl CF₂H Me 8.18 Me 4′-Cl

2′-Cl CF₂H Me 8.19 H 4′-Cl

5′-Cl CF₂H Me 8.20 Me 4′-Cl

5′-Cl CF₂H Me 8.21 H 4′-Cl

2′-Cl CF₂H Me 8.22 Me 4′-Cl

2′-Cl CF₂H Me 8.23 H 4′-Cl

5′-Cl CF₂H Me 8.24 Me 4′-Cl

5′-Cl CF₂H Me 8.25 H 4′-Cl

2′-Cl CF₂H Me 8.26 Me 4′-Cl

2′-Cl CF₃ Me 8.27 H 4′-Cl

5′-Cl CF₃ Me 8.28 Me 4′-Cl

5′-Cl CF₃ Me 8.29 H 4′-Cl

2′-Cl CF₃ Me 8.30 Me 4′-Cl

2′-Cl CF₃ Me 8.31 H 4′-Cl

5′-Cl CF₃ Me 8.32 Me 4′-Cl

5′-Cl CF₃ Me 8.33 H 4′-Cl

2′-Cl CF₃ Me 8.34 Me 4′-Cl

2′-Cl CF₃ Me 8.35 H 4′-Cl

2′-Cl CF₃ Me 8.36 Me 4′-Cl

5′-Cl CF₃ Me 8.37 H 4′-Cl

2′-Cl CF₃ Me 8.38 Me 4′-Cl

2′-Cl CF₃ Me 8.39 H 4′-Cl

5′-Cl CF₃ Me 8.40 Me 4′-Cl

5′-Cl CF₃ Me 8.41 H 4′-Cl

2′-Cl CF₃ Me 8.42 Me 4′-Cl

2′-Cl CF₃ Me 8.43 H 4′-Cl

5′-Cl CF₃ Me 8.44 Me 4′-Cl

5′-Cl CF₃ Me 8.45 H 4′-Cl

2′-Cl CF₃ Me 8.46 Me 4′-Cl

2′-Cl CF₃ Me 8.47 H 4′-Cl

5′-Cl CF₃ Me 8.48 Me 4′-Cl

5′-Cl CF₃ Me

TABLE 9 Compounds of Formula Ii (Ii)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 9.1 H 4′-Cl

2′-Cl CF₂H Me 9.2 Me 4′-Cl

2′-Cl CF₂H Me 9.3 H 4′-Cl

5′-Cl CF₂H Me 9.4 Me 4′-Cl

5′-Cl CF₂H Me 9.5 H 4′-Cl

2′-Cl CF₂H Me 9.6 Me 4′-Cl

2′-Cl CF₂H Me 9.7 H 4′-Cl

5′-Cl CF₂H Me 9.8 Me 4′-Cl

5′-Cl CF₂H Me 9.9 H 4′-Cl

2′-Cl CF₂H Me 9.10 Me 4′-Cl

2′-Cl CF₂H Me 9.11 H 4′-Cl

5′-Cl CF₂H Me 9.12 Me 4′-Cl

5′-Cl CF₂H Me 9.13 H 4′-Cl

2′-Cl CF₂H Me 9.14 Me 4′-Cl

2′-Cl CF₂H Me 9.15 H 4′-Cl

5′-Cl CF₂H Me 9.16 Me 4′-Cl

5′-Cl CF₂H Me 9.17 H 4′-Cl

2′-Cl CF₂H Me 9.18 Me 4′-Cl

2′-Cl CF₂H Me 9.19 H 4′-Cl

5′-Cl CF₂H Me 9.20 Me 4′-Cl

5′-Cl CF₂H Me 9.21 H 4′-Cl

2′-Cl CF₂H Me 9.22 Me 4′-Cl

2′-Cl CF₂H Me 9.23 H 4′-Cl

5′-Cl CF₂H Me 9.24 Me 4′-Cl

5′-Cl CF₂H Me 9.25 H 4′-Cl

2′-Cl CF₃ Me 9.26 Me 4′-Cl

2′-Cl CF₃ Me 9.27 H 4′-Cl

5′-Cl CF₃ Me 9.28 Me 4′-Cl

5′-Cl CF₃ Me 9.29 H 4′-Cl

2′-Cl CF₃ Me 9.30 Me 4′-Cl

2′-Cl CF₃ Me 9.31 H 4′-Cl

2′-Cl CF₃ Me 9.32 Me 4′-Cl

2′-Cl CF₃ Me 9.33 H 4′-Cl

2′-Cl CF₃ Me 9.34 Me 4′-Cl

2′-Cl CF₃ Me 9.35 H 4′-Cl

5′-Cl CF₃ Me 9.36 Me 4′-Cl

5′-Cl CF₃ Me 9.37 H 4′-Cl

2′-Cl CF₃ Me 9.38 Me 4′-Cl

2′-Cl CF₃ Me 9.39 H 4′-Cl

5′-Cl CF₃ Me 9.40 Me 4′-Cl

5′-Cl CF₃ Me 9.41 H 4′-Cl

2′-Cl CF₃ Me 9.42 Me 4′-Cl

2′-Cl CF₃ Me 9.43 H 4′-Cl

5′-Cl CF₃ Me 9.44 Me 4′-Cl

5′-Cl CF₃ Me 9.45 H 4′-Cl

2′-Cl CF₃ Me 9.46 Me 4′-Cl

2′-Cl CF₃ Me 9.47 H 4′-Cl

5′-Cl CF₃ Me 9.48 Me 4′-Cl

5′-Cl CF₃ Me

TABLE 10 Compounds of formula Ij Ij

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 10.1 H 4′-Cl

2′-Cl CF₂H Me 10.2 Me 4′-Cl

2′-Cl CF₂H Me 10.3 H 4′-Cl

5′-Cl CF₂H Me 10.4 Me 4′-Cl

5′-Cl CF₂H Me 10.5 H 4′-Cl

2′-Cl CF₂H Me 10.6 Me 4′-Cl

2′-Cl CF₂H Me 10.7 H 4′-Cl

5′-Cl CF₂H Me 10.8 Me 4′-Cl

5′-Cl CF₂H Me 10.9 H 4′-Cl

2′-Cl CF₂H Me 10.10 Me 4′-Cl

2′-Cl CF₂H Me 10.11 H 4′-Cl

5′-Cl CF₂H Me 10.12 Me 4′-Cl

5′-Cl CF₂H Me 10.13 H 4′-Cl

2′-Cl CF₂H Me 10.14 Me 4′-Cl

2′-Cl CF₂H Me 10.15 H 4′-Cl

5′-Cl CF₂H Me 10.16 Me 4′-Cl

5′-Cl CF₂H Me 10.17 H 4′-Cl

2′-Cl CF₂H Me 10.18 Me 4′-Cl

2′-Cl CF₂H Me 10.19 H 4′-Cl

5′-Cl CF₂H Me 10.20 Me 4′-Cl

5′-Cl CF₂H Me 10.21 H 4′-Cl

2′-Cl CF₂H Me 10.22 Me 4′-Cl

2′-Cl CF₂H Me 10.23 H 4′-Cl

5′-Cl CF₂H Me 10.24 Me 4′-Cl

5′-Cl CF₂H Me 10.25 H 4′-Cl

2′-Cl CF₃ Me 10.26 Me 4′-Cl

2′-Cl CF₃ Me 10.27 H 4′-Cl

5′-Cl CF₃ Me 10.28 Me 4′-Cl

5′-Cl CF₃ Me 10.29 H 4′-Cl

2′-Cl CF₃ Me 10.30 Me 4′-Cl

2′-Cl CF₃ Me 10.31 H 4′-Cl

5′-Cl CF₃ Me 10.32 Me 4′-Cl

5′-Cl CF₃ Me 10.33 H 4′-Cl

2′Cl CF₃ Me 10.34 Me 4′-Cl

2′-Cl CF₃ Me 10.35 H 4′-Cl

5′-Cl CF₃ Me 10.36 Me 4′-Cl

5′-Cl CF₃ Me 10.37 H 4′-Cl

2′-Cl CF₃ Me 10.38 Me 4′-Cl

2′-Cl CF₃ Me 10.39 H 4′-Cl

5′-Cl CF₃ Me 10.40 Me 4′-Cl

5′-Cl CF₃ Me 10.41 H 4′-Cl

2′-Cl CF₃ Me 10.42 Me 4′-Cl

2′-Cl CF₃ Me 10.43 H 4′-Cl

5′-Cl CF₃ Me 10.44 Me 4′-Cl

5′-Cl CF₃ Me 10.45 H 4′-Cl

2′-Cl CF₃ Me 10.46 Me 4′-Cl

2′-Cl CF₃ Me 10.47 H 4′-Cl

5′-Cl CF₃ Me 10.48 Me 4′-Cl

5′-Cl CF₃ Me

TABLE 11 Compounds of formula Ik (Ik)

Compound Number R₁ R₃ R₄ R₅ R₆ 11.1 H 4′-Cl

2′-Cl Cl 11.2 Me 4′-Cl

2′-Cl Cl 11.3 H 4′-Cl

5′-Cl Cl 11.4 Me 4′-Cl

5′-Cl Cl 11.5 H 4′-Cl

2′-Cl Br 11.6 Me 4′-Cl

2′-Cl Br 11.7 H 4′-Cl

5′-Cl Br 11.8 Me 4′-Cl

5′-Cl Br 11.9 H 4′-Cl

2′-Cl CF₃ 11.10 Me 4′-Cl

2′-Cl CF₃ 1.11 H 4′-Cl

5′-Cl CF₃ 11.12 Me 4′-Cl

5′-Cl CF₃ 11.13 H 4′-Cl

2′-Cl Cl 11.14 Me 4′-Cl

2′-Cl Cl 11.15 H 4′-Cl

5′-Cl Cl 11.16 Me 4′-Cl

5′-Cl Cl 11.17 H 4′-Cl

2′-Cl Br 11.18 Me 4′-Cl

2′-Cl Br 11.19 H 4′-Cl

5′-Cl Br 11.20 Me 4′-Cl

5′-Cl Br 11.21 H 4′-Cl

2′-Cl CF₃ 11.22 Me 4′-Cl

2′-Cl CF₃ 11.23 H 4′-Cl

5′-Cl CF₃ 11.24 Me 4′-Cl

5′-Cl CF₃ 11.25 H 4′-Cl

2′-Cl Cl 11.26 Me 4′-Cl

2′-Cl Cl 11.27 H 4′-Cl

5′-Cl Cl 11.28 Me 4′-Cl

5′-Cl Cl 11.29 H 4′-Cl

2′-Cl Br 11.30 Me 4′-Cl

2′-Cl Br 11.31 H 4′-Cl

5′-Cl Br 11.32 Me 4′-Cl

5′-Cl Br 11.33 H 4′-Cl

2′-Cl CF₃ 11.34 Me 4′-Cl

2′-Cl CF₃ 11.35 H 4′-Cl

5′-Cl CF₃ 11.36 Me 4′-Cl

5′-Cl CF₃ 11.37 H 4′-Cl

2′-Cl Cl 11.38 Me 4′-Cl

2′-Cl Cl 11.39 H 4′-Cl

5′-Cl Cl 11.40 Me 4′-Cl

5′-Cl Cl 11.41 H 4′-Cl

2′-Cl Br 11.42 Me 4′-Cl

2′-Cl Br 11.43 H 4′-Cl

5′-Cl Br 11.44 Me 4′-Cl

5′-Cl Br 11.45 H 4′-Cl

2′-Cl CF₃ 11.46 Me 4′-Cl

2′-Cl CF₃ 11.47 H 4′-Cl

5′-Cl CF₃ 11.48 Me 4′-Cl

5′-Cl CF₃ 11.49 H 4′-Cl

2′-Cl Cl 11.50 Me 4′-Cl

2′-Cl Cl 11.51 H 4′-Cl

5′-Cl Cl 11.52 Me 4′-Cl

5′-Cl Cl 11.53 H 4′-Cl

2′-Cl Br 11.54 Me 4′-Cl

2′-Cl Br 11.55 H 4′-Cl

5′-Cl Br 11.56 Me 4′-Cl

5′-Cl Br 11.57 H 4′-Cl

2′-Cl CF₃ 11.58 Me 4′-Cl

2′-Cl CF₃ 11.59 H 4′-Cl

5′-Cl CF₃ 11.60 Me 4′-Cl

5′-Cl CF₃ 11.61 H 4′-Cl

2′-Cl Cl 11.62 Me 4′-Cl

2′-Cl Cl 11.63 H 4′-Cl

5′-Cl Cl 11.64 Me 4′-Cl

5′-Cl Cl 11.65 H 4′-Cl

2′-Cl Br 11.66 Me 4′-Cl

2′-Cl Br 11.67 H 4′-Cl

5′-Cl Br 11.68 Me 4′-Cl

5′-Cl Br 11.69 H 4′-Cl

2′-Cl CF₃ 11.70 Me 4′-Cl

2′-Cl CF₃ 11.71 H 4′-Cl

5′-Cl CF₃ 11.72 Me 4′-Cl

5′-Cl CF₃

TABLE 12 Compounds of formula II (II)

Compound Number R₁ R₃ R₄ R₅ R₆ 12.1 H 4′-Cl

2′-Cl CF₂H 12.2 Me 4′-Cl

2′-Cl CF₂H 12.3 H 4′-Cl

5′-Cl CF₂H 12.4 Me 4′-Cl

5′-Cl CF₂H 12.5 H 4′-Cl

2′-Cl CF₃ 12.6 Me 4′-Cl

2′-Cl CF₃ 12.7 H 4′-Cl

5′-Cl CF₃ 12.8 Me 4′-Cl

5′-Cl CF₃ 12.9 H 4′-Cl

2′-Cl CF₂H 12.10 Me 4′-Cl

2′-Cl CF₂H 12.11 H 4′-Cl

5′-Cl CF₂H 12.12 Me 4′-Cl

5′-Cl CF₂H 12.13 H 4′-Cl

2′-Cl CF₃ 12.14 Me 4′-Cl

2′-Cl CF₃ 12.15 H 4′-Cl

5′-Cl CF₃ 12.16 Me 4′-Cl

5′-Cl CF₃ 12.17 H 4′-Cl

2′-Cl CF₂H 12.18 Me 4′-Cl

2′-Cl CF₂H 12.19 H 4′-Cl

5′-Cl CF₂H 12.20 Me 4′-Cl

5′-Cl CF₂H 12.21 H 4′-Cl

2′-Cl CF₃ 12.22 Me 4′-Cl

2′-Cl CF₃ 12.23 H 4′-Cl

5′-Cl CF₃ 12.24 Me 4′-Cl

5′-Cl CF₃ 12.25 H 4′-Cl

2′-Cl CF₂H 12.26 Me 4′-Cl

2′-Cl CF₂H 12.27 H 4′-Cl

5′-Cl CF₂H 12.28 Me 4′-Cl

5′-Cl CF₂H 12.29 H 4′-Cl

2′-Cl CF₃ 12.30 Me 4′-Cl

2′-Cl CF₃ 12.31 H 4′-Cl

5′-Cl CF₃ 12.32 Me 4′-Cl

5′-Cl CF₃ 12.33 H 4′-Cl

5′-Cl CF₂H 12.34 Me 4′-Cl

5′-Cl CF₂H 12.35 H 4′-Cl

2′-Cl CF₂H 12.36 Me 4′-Cl

2′-Cl CF₂H 12.37 H 4′-Cl

5′-Cl CF₃ 12.38 Me 4′-Cl

5′-Cl CF₃ 12.39 H 4′-Cl

2′-Cl CF₃ 12.40 Me 4′-Cl

2′-Cl CF₃ 12.41 H 4′-Cl

5′-Cl CF₂H 12.42 Me 4′-Cl

5′-Cl CF₂H 12.43 H 4′-Cl

2′-Cl CF₂H 12.44 Me 4′-Cl

2′-Cl CF₂H 12.45 H 4′-Cl

5′-Cl CF₃ 12.46 Me 4′-Cl

5′-Cl CF₃ 12.47 H 4′-Cl

2′-Cl CF₃ 12.48 Me 4′-Cl

2′-Cl CF₃

TABLE 13 compounds of formula Im: (Im)

Com- pound Number R₁ R₃ R₄ R₅ R₆ R₇ R₈ 13.1 H Cl

6′-H Me Me F 13.2 Me Cl

6′-H Me Me F 13.3 H Cl

5′-H Me Me F 13.4 Me Cl

5′-H Me Me F 13.5 H Cl

6′-H Me Me F 13.6 Me Cl

6′-H Me Me F 13.7 H Cl

5′-H Me Me F 13.8 Me Cl

5′-H Me Me F 13.9 H Cl

6′-H Me Me F 13.10 Me Cl

6′-H Me Me F 13.11 H Cl

5′-H Me Me F 13.12 Me Cl

5′-H Me Me F 13.13 H Cl

6′-H Me Me F 13.14 Me Cl

6′-H Me Me F 13.15 H Cl

5′-H Me Me F 13.16 Me Cl

5′-H Me Me F 13.17 H Cl

6′-H Me Me F 13.18 Me Cl

6′-H Me Me F 13.19 H Cl

5′-H Me Me F 13.20 Me Cl

5′-H Me Me F 13.21 H Cl

6′-H Me Me F 13.22 Me Cl

6′-H Me Me F 13.23 H Cl

5′-H Me Me F 13.24 Me Cl

5′-H Me Me F 13.25 H Cl

6′-H CF₂H Me H 13.26 Me Cl

6′-H CF₂H Me H 13.27 H Cl

5′-H CF₂H Me H 13.28 Me Cl

5′-H CF₂H Me H 13.29 H Cl

6′-H CF₂H Me H 13.30 Me Cl

6′-H CF₂H Me H 13.31 H Cl

5′-H CF₂H Me H 13.32 Me Cl

5′-H CF₂H Me H 13.33 H Cl

6′-H CF₂H Me H 13.34 Me Cl

6′-H CF₂H Me H 13.35 H Cl

5′-H CF₂H Me H 13.36 Me Cl

5′-H CF₂H Me H 13.37 H Cl

6′-H CF₂H Me H 13.38 Me Cl

6′-H CF₂H Me H 13.39 H Cl

5′-H CF₂H Me H 13.40 Me Cl

5′-H CF₂H Me H 13.41 H Cl

6′-H CF₂H Me H 13.42 Me Cl

6′-H CF₂H Me H 13.43 H Cl

5′-H CF₂H Me H 13.44 Me Cl

5′-H CF₂H Me H 13.45 H Cl

6′-H CF₂H Me H 13.46 Me Cl

6′-H CF₂H Me H 13.47 H Cl

5′-H CF₂H Me H 13.48 Me Cl

5′-H CF₂H Me H 13.49 H Cl

6′-H CF₃ Me H 13.50 Me Cl

6′-H CF₃ Me H 13.51 H Cl

5′-H CF₃ Me H 13.52 Me Cl

5′-H CF₃ Me H 13.53 H Cl

6′-H CF₃ Me H 13.54 Me Cl

6′-H CF₃ Me H 13.55 H Cl

5′-H CF₃ Me H 13.56 Me Cl

5′-H CF₃ Me H 13.57 H Cl

6′-H CF₃ Me H 13.58 Me Cl

6′-H CF₃ Me H 13.59 H Cl

5′-H CF₃ Me H 13.60 Me Cl

5′-H CF₃ Me H 13.61 H Cl

6′-H CF₃ Me H 13.62 Me Cl

6′-H CF₃ Me H 13.63 H Cl

5′-H CF₃ Me H 13.64 Me Cl

5′-H CF₃ Me H 13.65 H Cl

6′-H CF₃ Me H 13.66 Me Cl

6′-H CF₃ Me H 13.67 H Cl

5′-H CF₃ Me H 13.68 Me Cl

5′-H CF₃ Me H 13.69 H Cl

6′-H CF₃ Me H 13.70 Me Cl

6′-H CF₃ Me H 13.71 H Cl

5′-H CF₃ Me H 13.72 Me Cl

5′-H CF₃ Me H

TABLE 14 compound of formula In (In)

Compound Number R₁ R₃ R₄ R₅ R₆ 14.1 H Cl

6′-H CF₃ 14.2 Me Cl

5′-H CF₃ 14.3 H Cl

6′-H CF₃ 14.4 Me Cl

5′-H CF₃ 14.5 H Cl

6′-H CF₃ 14.6 Me Cl

5′-H CF₃ 14.7 H Cl

6′-H CF₃ 14.8 Me Cl

5′-H CF₃ 14.9 H Cl

6′-H CF₃ 14.10 Me Cl

5′-H CF₃ 14.11 H Cl

6′-H CF₃ 14.12 Me Cl

5′-H CF₃Tables 15-17: Compounds of Formula II

The invention is further illustrated by the preferred individualcompounds of formula (II) listed below in Tables 15-17. Characterisingdata is given in Table 21.

TABLE 15 Compounds of formula (IIa) (IIa),

Cpd No. R₁ R₃ R_(4A) R₅ A Z1.1 H Cl Br H3-difluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1.2 Me Cl Br H3-difluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1.3 H Br Br H3-difluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1.4 Me Br Br H3-difluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1.5 H Cl Br H3-trifluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1.6 Me Cl Br H3-trifluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1.7 H Br Br H3-trifluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1.8 Me Br Br H3-trifluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1.9 H Cl Br H3-difluoromethyl-1-methyl-pyrrol-4-yl Z1.10 Me Cl Br H3-difluoromethyl-1-methyl-pyrrol-4-yl Z1.11 H Cl Br H3-difluoromethyl-1-methyl-1H-triazol- 4-yl Z1.12 Me Cl Br H3-difluoromethyl-1-methyl-1H-triazol- 4-yl Z1.13 H Cl Br H4-difluoromethyl-2-methyl-thiazol-5-yl Z1.14 Me Cl Br H4-difluoromethyl-2-methyl-thiazol-5-yl Z1.15 H Cl Br H2-chloro-pyridyl-3-yl Z1.16 Me Cl Br H 2-chloro-pyridyl-3-yl Z1.17 H ClBr H 2-difluoromethyl-phenyl Z1.18 Me Cl Br H 2-difluoromethyl-phenylZ1.19 H Cl Br H 2-trifluoromethyl-phenyl Z1.20 Me Cl Br H2-trifluoromethyl-phenyl

TABLE 16 Compounds of formula IIb (IIb)

Cpd No. R₁ R₃ R_(4A) R₅ A Z1.21 H 4′-Cl 5′-Br 2′-Cl3-difluoromethyl-1-methyl-1H- pyrazol-4-yl Z1.22 Me 4′-Cl 5′-Br 2′-Cl3-difluoromethyl-1-methyl-1H- pyrazol-4-yl Z1.23 H 4′-Cl 2′-Br 5′-Cl3-difluoromethyl-1-methyl-1H- pyrazol-4-yl Z1.24 Me 4′-Cl 2′-Br 5′-Cl3-difluoromethyl-1-methyl-1H- pyrazol-4-yl

TABLE 17 Compounds of formula IIc: (IIc)

Cpd No. R₁ R₃ R_(4A) R₅ A Z1.25 H Cl 5′-Br 6′-H3-difluoromethyl-1-methyl-1H-pyra- zol-4-yl Z1.26 Me Cl 5-Br 6′-H3-difluoromethyl-1-methyl-1H-pyra- zol-4-yl Z1.27 H Cl 6′-Br 5′-H3-difluoromethyl-1-methyl-1H-pyra- zol-4-yl Z1.28 Me Cl 6′-Br 6′-H3-difluoromethyl-1-methyl-1H-pyra- zol-4-ylTables 18-20: Compounds of Formula III

The invention is further illustrated by the preferred individualcompounds of formula (III) listed below in Tables 18-20. Characterisingdata is given in Table 21.

TABLE 18 Compounds of formula (IIIa) (IIIa),

Cpd No. R₁ R₃ R_(4A) R₅ Z2.1 H Cl Br H Z2.2 Me Cl Br H Z2.3 H Br Br HZ2.4 Me Br Br H

TABLE 19 Compounds of formula IIIb (IIIb)

Cpd No. R₁ R₃ R_(4A) R₅ Z2.5 H 4′-Cl 5′-Br 2′-Cl Z2.6 Me 4′-Cl 5′-Br2′-Cl Z2.7 H 4′-Cl 2′-Br 5′-Cl Z2.8 Me 4′-Cl 2′-Br 5′-Cl

TABLE 20 Compounds of formula IIIc: (IIIc)

Cpd No. R₁ R₃ R_(4A) R₅ Z2.9 H Cl 5′-Br 6′-H Z2.10 Me Cl 5-Br 6′-H Z2.11H Cl 6′-Br 5′-H Z2.12 Me Cl 6′-Br 5′-HTable 21: Characterising Data

Table 21 shows selected melting point and selected NMR data forcompounds of Tables 1 to 20. CDCl₃ was used as the solvent for NMRmeasurements, unless otherwise stated. If a mixture of solvents waspresent, this is indicated as, for example: CDCl₃/d₆-DMSO). No attemptis made to list all characterising data for compounds of Tables 1 to 20.In Table 21 and throughout the description that follows, temperaturesare given in degrees Celsius; “NMR” means nuclear magnetic resonancespectrum; MS stands for mass spectrum; “%” is percent by weight, unlesscorresponding concentrations are indicated in other units. The followingabbreviations are used throughout this description:

m.p. = melting point b.p. = boiling point. S = singlet br = broad d =doublet dd = doublet of doublets t = triplet q = quartet m = multipletppm = parts per million

TABLE 21 Compound m.p./ Number ¹H-NMR data: (ppm/multiplicity/number ofHs). (° C.) 1.26 0.79/m/2H; 0.88/m/2H; 1.25/d/3H; 1.42/m/1H; resin3.0/d/2H; 3.9/s/3H; 4.38/m/1H; 6.25/m/1H; 6.87/s/1H; 6.89/t/1H;7.85/s/1H 1.38 1.27/d/3H; 3.09/d/2H; 3.91/s/3H; 4.42/m/1H; resin6.22/s/1H; 6.87/t/1H; 7.05/s/1H; 7.35/m/2H; 7.48/m/2H; 7.9/s/1H 1.42 —87-89 1.46 1.28/d/3H; 3.08/d/2H; 3.88/s/3H; 4.45/m/1H; wax 6.38/s/1H;6.9/t/1H; 7.05/m/2H; 7.45/m/2H; 7.88/s/1H 6.2 — 100-102 6.14 — 130-1326.18 — 138-140 6.22 — 139-141 7.28 — 135-137 7.30 — 73-77 7.32 — resin7.46 — oil 7.70 1.31/d/3H; 2.9/m/2H (diastereotopic protons); oil3.97/s/3H; 4.55/m/1H; 5.98/d (broad)/1H; 7.12/t/2H; 7.53/m/2H;7.87/s/1H) 7.72 — 126-130 12.6 — 166-168 12.30 — 172-174Tables 1 to 14: Compounds of Formula IAa

The invention is further illustrated by the preferred individualcompounds of formula (IAa) listed below in Tables 1a to 14a.

TABLE 1a Compounds of formula IAa (IAa)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ R₈ 1a.1 H Cl

H Me Me F 1a.2 Me Cl

H Me Me F 1a.3 H Br

H Me Me F 1a.4 Me Br

H Me Me F 1a.5 H Cl

H Me Me F 1a.6 Me Cl

H Me Me F 1a.7 H Br

H Me Me F 1a.8 Me Br

H Me Me F 1a.9 H Cl

H Me Me F 1a.10 Me Cl

H Me Me F 1a.11 H Br

H Me Me F 1a.12 Me Br

H Me Me F 1a.13 H Cl

H Me Me F 1a.14 Me Cl

H Me Me F 1a.15 H Br

H Me Me F 1a.16 Me Br

H Me Me F 1a.17 H Cl

H Me Me F 1a.18 Me Cl

H Me Me F 1a.19 H Br

H Me Me F 1a.20 Me Br

H Me Me F 1a.21 H Cl

H Me Me F 1a.22 Me Cl

H Me Me F 1a.23 H Br

H Me Me F 1a.24 Me Br

H Me Me F 1a.25 H Cl

H CF₂H Me H 1a.26 Me Cl

H CF₂H Me H 1a.27 H Br

H CF₂H Me H 1a.28 Me Br

H CF₂H Me H 1a.29 H Cl

H CF₂H Me H 1a.30 Me Cl

H CF₂H Me H 1a.31 H Br

H CF₂H Me H 1a.32 Me Br

H CF₂H Me H 1a.33 H Cl

H CF₂H Mr H 1a.34 Me Cl

H CF₂H Me H 1a.35 H Br

H CF₂H Me H 1a.36 Me Br

H CF₂H Me H 1a.37 H Cl

H CF₂H Me H 1a.38 Me Cl

H CF₂H Me H 1a.39 H Br

H CF₂H Me H 1a.40 Me Br

H CF₂H Me H 1a.41 H Cl

H CF₂H Me H 1a.42 Me Cl

H CF₂H Me H 1a.43 H Br

H CF₂H Me H 1a.44 Me Br

H CF₂H Me H 1a.45 H Cl

H CF₂H Me H 1a.46 Me Cl

H CF₂H Me H 1a.47 H Br

H CF₂H Me H 1a.48 Me Br

H CF₂H Me H 1a.49 H Cl

H CF₃ Me H 1a.50 Me Cl

H CF₃ Me H 1a.51 H Br

H CF₃ Me H 1a.52 Me Br

H CF₃ Me H 1a.53 H Cl

H CF₃ Me H 1a.54 Me Cl

H CF₃ Me H 1a.55 H Br

H CF₃ Me H 1a.56 Me Br

H CF₃ Me H 1a.57 H Cl

H CF₃ Me H 1a.58 Me Cl

H CF₃ Me H 1a.59 H Br

H CF₃ Me H 1a.60 Me Br

H CF₃ Me H 1a.61 H Cl

H CF₃ Me H 1a.62 Me Cl

H CF₃ Me H 1a.63 H Br

H CF₃ Me H 1a.64 Me Br

H CF₃ Me H 1a.65 H Cl

H CF₃ Me H 1a.66 Me Cl

H CF₃ Me H 1a.67 H Br

H CF₃ Me H 1a.68 Me Br

H CF₃ Me H 1a.69 H Cl

H CF₃ Me H 1a.70 Me Cl

H CF₃ Me H 1a.71 H Br

H CF₃ Me H 1a.72 Me Br

H CF₃ Me H

TABLE 2a Compound of formula IAb (IAb)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 2a.1 H Cl

H CF₂H Me 2a.2 Me Cl

H CF₂H Me 2a.3 H Br

H CF₂H Me 2a.4 Me Br

H CF₂H Me 2a.5 H Cl

H CF₂H Me 2a.6 Me Cl

H CF₂H Me 2a.7 H Br

H CF₂H Me 2a.8 Me Cl

H CF₂H Me 2a.9 H Cl

H CF₂H Me 2a.10 Me Cl

H CF₂H Me 2a.11 H Br

H CF₂H Me 2a.12 Me Br

H CF₂H Me 2a.13 H Cl

H CF₂H Me 2a.14 Me Cl

H CF₂H Me 2a.15 H Br

H CF₂H Me 2a.16 Me Br

H CF₂H Me 2a.17 H Cl

H CF₂H Me 2a.18 Me Cl

H CF₂H Me 2a.19 H Br

H CF₂H Me 2a.20 Me Br

H CF₂H Me 2a.21 H Cl

H CF₂H Me 2a.22 Me Cl

H CF₂H Me 2a.23 H Br

H CF₂H Me 2a.24 Me Br

H CF₂H Me 2a.25 H Cl

H CF₃ Me 2a.26 Me Cl

H CF₃ Me 2a.27 H Br

H CF₃ Me 2a.28 Me Br

H CF₃ Me 2a.29 H Cl

H CF₃ Me 2a.30 Me Cl

H CF₃ Me 2a.31 H Br

H CF₃ Me 2a.32 Me Cl

H CF₃ Me 2a.33 H Cl

H CF₃ Me 2a.34 Me Cl

H CF₃ Me 2a.35 H Br

H CF₃ Me 2a.36 Me Br

H CF₃ Me 2a.37 H Cl

H CF₃ Me 2a.38 Me Cl

H CF₃ Me 2a.39 H Br

H CF₃ Me 2a.40 Me Br

H CF₃ Me 2a.41 H Cl

H CF₃ Me 2a.42 Me Cl

H CF₃ Me 2a.43 H Br

H CF₃ Me 2a.44 Me Br

H CF₃ Me 2a.45 H Cl

H CF₃ Me 2a.46 Me Cl

H CF₃ Me 2a.47 H Br

H CF₃ Me 2a.48 Me Br

H CF₃ Me

TABLE 3a Compounds of Formula IAc (IAc)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 3a.1 H Cl

H CF₂H Me 3a.2 Me Cl

H CF₂H Me 3a.3 H Br

H CF₂H Me 3a.4 Me Br

H CF₂H Me 3a.5 H Cl

H CF₂H Me 3a.6 Me Cl

H CF₂H Me 3a.7 H Br

H CF₂H Me 3a.8 Me Cl

H CF₂H Me 3a.9 H Cl

H CF₂H Me 3a.10 Me Cl

H CF₂H Me 3a.11 H Br

H CF₂H Me 3a.12 Me Br

H CF₂H Me 3a.13 H Cl

H CF₂H Me 3a.14 Me Cl

H CF₂H Me 3a.15 H Br

H CF₂H Me 3a.16 Me Br

H CF₂H Me 3a.17 H Cl

H CF₂H Me 3a.18 Me Cl

H CF₂H Me 3a.19 H Br

H CF₂H Me 3a.20 Me Br

H CF₂H Me 3a.21 H Cl

H CF₂H Me 3a.22 Me Cl

H CF₂H Me 3a.23 H Br

H CF₂H Me 3a.24 Me Br

H CF₂H Me 3a.25 H Cl

H CF₃ Me 3a.26 Me Cl

H CF₃ Me 3a.27 H Br

H CF₃ Me 3a.28 Me Br

H CF₃ Me 3a.29 H Cl

H CF₃ Me 3a.30 Me Cl

H CF₃ Me 3a.31 H Br

H CF₃ Me 3a.32 Me Cl

H CF₃ Me 3a.33 H Cl

H CF₃ Me 3a.34 Me Cl

H CF₃ Me 3a.35 H Br

H CF₃ Me 3a.36 Me Br

H CF₃ Me 3a.37 H Cl

H CF₃ Me 3a.38 Me Cl

H CF₃ Me 3a.39 H Br

H CF₃ Me 3a.40 Me Br

H CF₃ Me 3a.41 H Cl

H CF₃ Me 3a.42 Me Cl

H CF₃ Me 3a.43 H Br

H CF₃ Me 3a.44 Me Br

H CF₃ Me 3a.45 H Cl

H CF₃ Me 3a.46 Me Cl

H CF₃ Me 3a.47 H Br

H CF₃ Me 3a.48 Me Br

H CF₃ Me

TABLE 4a Compounds of formula IAd (IAd)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 4a.1 H Cl

H CF₂H Me 4a.2 Me Cl

H CF₂H Me 4a.3 H Br

H CF₂H Me 4a.4 Me Br

H CF₂H Me 4a.5 H Cl

H CF₂H Me 4a.6 Me Cl

H CF₂H Me 4a.7 H Br

H CF₂H Me 4a.8 Me Cl

H CF₂H Me 4a.9 H Cl

H CF₂H Me 4a.10 Me Cl

H CF₂H Me 4a.11 H Br

H CF₂H Me 4a.12 Me Br

H CF₂H Me 4a.13 H Cl

H CF₂H Me 4a.14 Me Cl

H CF₂H Me 4a.15 H Br

H CF₂H Me 4a.16 Me Br

H CF₂H Me 4a.17 H Cl

H CF₂H Me 4a.18 Me Cl

H CF₂H Me 4a.19 H Br

H CF₂H Me 4a.20 Me Br

H CF₂H Me 4a.21 Me Cl

H CF₂H Me 4a.22 Me Cl

H CF₂H Me 4a.23 H Br

H CF₂H Me 4a.24 Me Br

H CF₂H Me 4a.25 H Cl

H CF₃ Me 4a.26 Me Cl

H CF₃ Me 4a.27 H Br

H CF₃ Me 4a.28 Me Br

H CF₃ Me 4a.29 H Cl

H CF₃ Me 4a.30 Me Cl

H CF₃ Me 4a.31 H Br

H CF₃ Me 4a.32 Me Cl

H CF₃ Me 4a.33 H Cl

H CF₃ Me 4a.34 Me Cl

H CF₃ Me 4a.35 H Br

H CF₃ Me 4a.36 Me Br

H CF₃ Me 4a.37 H Cl

H CF₃ Me 4a.38 Me Cl

H CF₃ Me 4a.39 H Br

H CF₃ Me 4a.40 Me Br

H CF₃ Me 4a.41 H Cl

H CF₃ Me 4a.42 Me Cl

H CF₃ Me 4a.43 H Br

H CF₃ Me 4a.44 Me Br

H CF₃ Me 4a.45 H Cl

H CF₃ Me 4a.46 Me Cl

H CF₃ Me 4a.47 H Br

H CF₃ me 4a.48 Me Br

H CF₃ Me

TABLE 5a Compounds of formula IAe (IAe)

Compound Number R₁ R₃ R₄ R₅ R₆ 5a.1 H Cl

H Cl 5a.2 Me Cl

H Cl 5a.3 H Cl

H Br 5a.4 Me Cl

H Br 5a.5 H Cl

H CF₃ 5a.6 Me Cl

H CF₃ 5a.7 H Br

H Cl 5a.8 Me Br

H Cl 5a.9 H Br

H Br 5a.10 Me Br

H Br 5a.11 H Br

H CF₃ 5a.12 Me Br

H CF₃ 5a.13 H Cl

H Cl 5a.14 Me Cl

H Cl 5a.15 H Cl

H Br 5a.16 Me Cl

H Br 5a.17 H Cl

H CF₃ 5a.18 Me Cl

H CF₃ 5a.19 H Br

H Cl 5a.20 Me Br

H Cl 5a.21 H Br

H Br 5a.22 Me Br

H Br 5a.23 H Br

H CF₃ 5a.24 Me Br

H CF₃ 5a.25 H Cl

H Cl 5a.26 Me Cl

H Cl 5a.27 H Cl

H Br 5a.28 Me Cl

H Br 5a.29 H Cl

H CF₃ 5a.30 Me Cl

H CF₃ 5a.31 H Br

H Cl 5a.32 Me Br

H Cl 5a.33 H Br

H Br 5a.34 Me Br

H Br 5a.35 H Br

H CF₃ 5a.36 Me Br

H CF₃ 5a.37 H Cl

H Cl 5a.38 Me Cl

H Cl 5a.39 H Cl

H Br 5a.40 Me Cl

H Br 5a.41 H Cl

H CF₃ 5a.42 Me Cl

H CF₃ 5a.43 H Br

H Cl 5a.44 Me Br

H Cl 5a.45 H Br

H Br 5a.46 Me Br

H Br 5a.47 H Br

H CF₃ 5a.48 Me Br

H CF₃ 5a.49 H Cl

H Cl 5a.50 Me Cl

H Cl 5a.51 H Cl

H Br 5a.52 Me Cl

H Br 5a.53 H Cl

H CF₃ 5a.54 Me Cl

H CF₃ 5a.55 H Br

H Cl 5a.56 Me Br

H Cl 5a.57 H Br

H Br 5a.58 Me Br

H Br 5a.59 H Br

H CF₃ 5a.60 Me Br

H CF₃ 5a.61 H Cl

H Cl 5a.62 Me Cl

H Cl 5a.63 H Cl

H Br 5a.64 Me Cl

H Br 5a.65 H Cl

H CF₃ 5a.66 Me Cl

H CF₃ 5a.67 H Br

H Cl 5a.68 Me Br

H Cl 5a.69 H Br

H Br 5a.70 Me Br

H Br 5a.71 H Br

H CF₃ 5a.72 Me Br

H CF₃

TABLE 6a Compounds of formula IAf (IAf)

Compound Number R₁ R₃ R₄ R₅ R₆ 6a.1 H Cl

H CF₂H 6a.2 Me Cl

H CF₃ 6a.3 H Br

H CF₂H 6a.4 Me Br

H CF₃ 6a.5 H Cl

H CF₂H 6a.6 Me Cl

H CF₃ 6a.7 H Br

H CF₂H 6a.8 Me Br

H CF₃ 6a.9 H Cl

H CF₂H 6a.10 Me Cl

H CF₃ 6a.11 H Br

H CF₂H 6a.12 Me Br

H CF₃ 6a.13 H Cl

H CF₂H 6a.14 Me Cl

H CF₃ 6a.15 H Br

H CF₂H 6a.16 Me Br

H CF₃ 6a.17 H Cl

H CF₂H 6a.18 Me Cl

H CF₃ 6a.19 H Br

H CF₂H 6a.20 Me Br

H CF₃ 6a.21 H Cl

H CF₂H 6a.22 Me Cl

H CF₃ 6a.23 H Br

H CF₂H 6a.24 Me Br

H CF₃

TABLE 7a Compounds of formula IAg (IAg)

Com- pound Number R₁ R₃ R₄ R₅ R₆ R₇ R₈ 7a.1 H 4′-Cl

2′-Cl Me Me F 7a.2 Me 4′-Cl

2′-Cl Me Me F 7a.3 H 4′-Cl

5′-Cl Me Me F 7a.4 Me 4′-Cl

5′-Cl Me Me F 7a.5 H 4′-Cl

2′-Cl Me Me F 7a.6 Me 4′-Cl

2′-Cl Me Me F 7a.7 H 4′-Cl

5′-Cl Me Me F 7a.8 Me 4′-Cl

5′-Cl Me Me F 7a.9 H 4′-Cl

2′-Cl Me Me F 7a.10 Me 4′-Cl

2′-Cl Me Me F 7a.11 H 4′-Cl

5′-Cl Me Me F 7a.12 Me 4′-Cl

5′-Cl Me Me F 7a.13 H 4′-Cl

2′-Cl Me Me F 7a.14 Me 4′-Cl

2′-Cl Me Me F 7a.15 H 4′-Cl

5′-Cl Me Me F 7a.16 Me 4′-Cl

5′-Cl Me Me F 7a.17 H 4′-Cl

2′-Cl Me Me F 7a.18 Me 4′-Cl

2′-Cl Me Me F 7a.19 H 4′-Cl

5′-Cl Me Me F 7a.20 Me 4′-Cl

5′-Cl Me Me F 7a.21 H 4′-Cl

2′-Cl Me Me F 7a.22 Me 4′-Cl

2′-Cl Me Me F 7a.23 H 4′-Cl

5′-Cl Me Me F 7a.24 Me 4′-Cl

5′-Cl Me Me F 7a.25 H 4′-Cl

2′-Cl CF₂H Me H 7a.26 Me 4′-Cl

2′-Cl CF₂H Me H 7a.27 H 4′-Cl

5′-Cl CF₂H Me H 7a.28 Me 4′-Cl

5′-Cl CF₂H Me H 7a.29 H 4′-Cl

2′-Cl CF₂H Me H 7a.30 Me 4′-Cl

2′-Cl CF₂H Me H 7a.31 H 4′-Cl

5′-Cl CF₂H Me H 7a.32 Me 4′-Cl

5′-Cl CF₂H Me H 7a.33 H 4′-Cl

2′-Cl CF₂H Me H 7a.34 Me 4′-Cl

2′-Cl CF₂H Me H 7a.35 H 4′-Cl

5′-Cl CF₂H Me H 7a.36 Me 4′-Cl

5′-Cl CF₂H Me H 7a.37 H 4′-Cl

2′-Cl CF₂H Me H 7a.38 Me 4′-Cl

2′-Cl CF₂H Me H 7a.39 H 4′-Cl

5′-Cl CF₂H Me H 7a.40 Me 4′-Cl

5′-Cl CF₂H Me H 7a.41 H 4′-Cl

2′-Cl CF₂H Me H 7a.42 Me 4′-Cl

2′-Cl CF₂H Me H 7a.43 H 4′-Cl

5′-Cl CF₂H Me H 7a.44 Me 4′-Cl

5′-Cl CF₂H Me H 7a.45 H 4′-Cl

2′-Cl CF₂H Me H 7a.46 Me 4′-Cl

2′-Cl CF₂H Me H 7a.47 H 4′-Cl

5′-Cl CF₂H Me H 7a.48 Me 4′-Cl

5′-Cl CF₂H Me H 7a.49 H 4′-Cl

2′-Cl CF₃ Me H 7a.50 Me 4′-Cl

2′-Cl CF₃ Me H 7a.51 H 4′-Cl

5′-Cl CF₃ Me H 7a.52 Me 4′-Cl

5′-Cl CF₃ Me H 7a.53 H 4′-Cl

2′-Cl CF₃ Me H 7a.54 Me 4′-Cl

2′-Cl CF₃ Me H 7a.55 H 4′-Cl

5′-Cl CF₃ Me H 7a.56 Me 4′-Cl

5′-Cl CF₃ Me H 7a.57 H 4′-Cl

2′-Cl CF₃ Me H 7a.58 Me 4′-Cl

2′-Cl CF₃ Me H 7a.59 H 4′-Cl

5′-Cl CF₃ Me H 7a.60 Me 4′-Cl

5′-Cl CF₃ Me H 7a.61 H 4′-Cl

2′-Cl CF₃ Me H 7a.62 Me 4′-Cl

2′-Cl CF₃ Me H 7a.63 H 4′-Cl

5′-Cl CF₃ Me H 7a.64 Me 4′-Cl

5′-Cl CF₃ Me H 7a.65 H 4′-Cl

2′-Cl CF₃ Me H 7a.66 Me 4′-Cl

2′-Cl CF₃ Me H 7a.67 H 4′-Cl

5′-Cl CF₃ Me H 7a.68 Me 4′-Cl

5′-Cl CF₃ Me H 7a.69 H 4′-Cl

2′-Cl CF₃ Me H 7a.70 Me 4′-Cl

2′-Cl CF₃ Me H 7a.71 H 4′-Cl

5′-Cl CF₃ Me H 7a.72 Me 4′-Cl

5′-Cl CF₃ Me H

TABLE 8a Compound of formula IAh (IAh)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 8a.1 H 4′-Cl

2′-Cl CF₂H Me 8a.2 Me 4′-Cl

2′-Cl CF₂H Me 8a.3 H 4′-Cl

5′-Cl CF₂H Me 8a.4 Me 4′-Cl

5′-Cl CF₂H Me 8a.5 H 4′-Cl

2′-Cl CF₂H Me 8a.6 Me 4′-Cl

2′-Cl CF₂H Me 8a.7 H 4′-Cl

5′-Cl CF₂H Me 8a.8 Me 4′-Cl

5′-Cl CF₂H Me 8a.9 H 4′-Cl

2′-Cl CF₂H Me 8a.10 Me 4′-Cl

2′-Cl CF₂H Me 8a.11 H 4′-Cl

5′-Cl CF₂H Me 8a.12 Me 4′-Cl

5′-Cl CF₂H Me 8a.13 H 4′-Cl

2′-Cl CF₂H Me 8a.14 Me 4′-Cl

2′-Cl CF₂H Me 8a.15 H 4′-Cl

5′-Cl CF₂H Me 8a.16 Me 4′-Cl

5′-Cl CF₂H Me 8a.17 H 4′-Cl

2′-Cl CF₂H Me 8a.18 Me 4′-Cl

2′-Cl CF₂H Me 8a.19 H 4′-Cl

5′-Cl CF₂H Me 8a.20 Me 4′-Cl

5′-Cl CF₂H Me 8a.21 H 4′-Cl

2′-Cl CF₂H Me 8a.22 Me 4′-Cl

2′-Cl CF₂H Me 8a.23 H 4′-Cl

5′-Cl CF₂H Me 8a.24 Me 4′-Cl

5′-Cl CF₂H Me 8a.25 H 4′-Cl

2′-Cl CF₃ Me 8a.26 Me 4′-Cl

2′-Cl CF₃ Me 8a.27 H 4′-Cl

5′-Cl CF₃ Me 8a.28 Me 4′-Cl

5′-Cl CF₃ Me 8a.29 H 4′-Cl

2′-Cl CF₃ Me 8a.30 Me 4′-Cl

2′-Cl CF₃ Me 8a.31 H 4′-Cl

5′-Cl CF₃ Me 8a.32 Me 4′-Cl

5′-Cl CF₃ Me 8a.33 H 4′-Cl

2′-Cl CF₃ Me 8a.34 Me 4′-Cl

2′-Cl CF₃ Me 8a.35 H 4′-Cl

5′-Cl CF₃ Me 8a.36 Me 4′-Cl

5′-Cl CF₃ Me 8a.37 H 4′-Cl

2′-Cl CF₃ Me 8a.38 Me 4′-Cl

2′-Cl CF₃ Me 8a.39 H 4′-Cl

5′-Cl CF₃ Me 8a.40 Me 4′-Cl

5′-Cl CF₃ Me 8a.41 H 4′-Cl

2′-Cl CF₃ Me 8a.42 Me 4′-Cl

2′-Cl CF₃ Me 8a.43 H 4′-Cl

5′-Cl CF₃ Me 8a.44 Me 4′-Cl

5′-Cl CF₃ Me 8a.45 H 4′-Cl

2′-Cl CF₃ Me 8a.46 Me 4′-Cl

2′-Cl CF₃ Me 8a.47 H 4′-Cl

5′-Cl CF₃ Me 8a.48 Me 4′-Cl

5′-Cl CF₃ Me

TABLE 9a Compounds of Formula IAi (IAi)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 9a.1 H 4′-Cl

2′-Cl CF₂H Me 9a.2 Me 4′-Cl

2′-Cl CF₂H Me 9a.3 H 4′-Cl

5′-Cl CF₂H Me 9a.4 Me 4′-Cl

5′-Cl CF₂H Me 9a.5 H 4′-Cl

2′-Cl CF₂H Me 9a.6 Me 4′-Cl

2′-Cl CF₂H Me 9a.7 H 4′-Cl

5′-Cl CF₂H Me 9a.8 Me 4′-Cl

5′-Cl CF₂H Me 9a.9 H 4′-Cl

2′-Cl CF₂H Me 9a.10 Me 4′-Cl

2′-Cl CF₂H Me 9a.11 H 4′-Cl

5′-Cl CF₂H Me 9a.12 Me 4′-Cl

5′-Cl CF₂H Me 9a.13 H 4′-Cl

2′-Cl CF₂H Me 9a.14 Me 4′-Cl

2′-Cl CF₂H Me 9a.15 H 4′-Cl

5′-Cl CF₂H Me 9a.16 Me 4′-Cl

5′-Cl CF₂H Me 9a.17 H 4′-Cl

2′-Cl CF₂H Me 9a.18 Me 4′-Cl

2′-Cl CF₂H Me 9a.19 H 4′-Cl

5′-Cl CF₂H Me 9a.20 Me 4′-Cl

5′-Cl CF₂H Me 9a.21 H 4′-Cl

2′-Cl CF₂H Me 9a.22 Me 4′-Cl

2′-Cl CF₂H Me 9a.23 H 4′-Cl

5′-Cl CF₂H Me 9a.24 Me 4′-Cl

5′-Cl CF₂H Me 9a.25 H 4′-Cl

2′-Cl CF₃ Me 9a.26 Me 4′-Cl

2′-Cl CF₃ Me 9a.27 H 4′-Cl

5′-Cl CF₃ Me 9a.28 Me 4′-Cl

5′-Cl CF₃ Me 9a.29 H 4′-Cl

2′-Cl CF₃ Me 9a.30 Me 4′-Cl

2′-Cl CF₃ Me 9a.31 H 4′-Cl

5′-Cl CF₃ Me 9a.32 Me 4′-Cl

5′-Cl CF₃ Me 9a.33 H 4′-Cl

2′-Cl CF₃ Me 9a.34 Me 4′-Cl

2′-Cl CF₃ Me 9a.35 H 4′-Cl

5′-Cl CF₃ Me 9a.36 Me 4′-Cl

5′-Cl CF₃ Me 9a.37 H 4′-Cl

2′-Cl CF₃ Me 9a.38 Me 4′-Cl

2′-Cl CF₃ Me 9a.39 H 4′-Cl

5′-Cl CF₃ Me 9a.40 Me 4′-Cl

5′-Cl CF₃ Me 9a.41 H 4′-Cl

2′-Cl CF₃ Me 9a.42 Me 4′-Cl

2′-Cl CF₃ Me 9a.43 H 4′-Cl

5′-Cl CF₃ Me 9a.44 Me 4′-Cl

5′-Cl CF₃ Me 9a.45 H 4′-Cl

2′-Cl CF₃ Me 9a.46 Me 4′-Cl

2′-Cl CF₃ Me 9a.47 H 4′-Cl

5′-Cl CF₃ Me 9a.48 Me 4′-Cl

5′-Cl CF₃ Me

TABLE 10a Compounds of formula IAj (IAj)

Compound Number R₁ R₃ R₄ R₅ R₆ R₇ 10a.1 H 4′-Cl

2′-Cl CF₂H Me 10a.2 Me 4′-Cl

2′-Cl CF₂H Me 10a.3 H 4′-Cl

5′-Cl CF₂H Me 10a.4 Me 4′-Cl

5′-Cl CF₂H Me 10a.5 H 4′-Cl

2′-Cl CF₂H Me 10a.6 Me 4′-Cl

2′-Cl CF₂H Me 10a.7 H 4′-Cl

5′-Cl CF₂H Me 10a.8 Me 4′-Cl

5′-Cl CF₂H Me 10a.9 H 4′-Cl

2′-Cl CF₂H Me 10a.10 Me 4′-Cl

2′-Cl CF₂H Me 10a.11 H 4′-Cl

5′-Cl CF₂H Me 10a.12 Me 4′-Cl

5′-Cl CF₂H Me 10a.13 H 4′-Cl

2′-Cl CF₂H Me 10a.14 Me 4′-Cl

2′-Cl CF₂H Me 10a.15 H 4′-Cl

5′-Cl CF₂H Me 10a.16 Me 4′-Cl

5′-Cl CF₂H Me 10a.17 H 4′-Cl

2′-Cl CF₂H Me 10a.18 Me 4′-Cl

2′-Cl CF₂H Me 10a.19 H 4′-Cl

5′-Cl CF₂H Me 10a.20 Me 4′-Cl

5′-Cl CF₂H Me 10a.21 H 4′-Cl

2′-Cl CF₂H Me 10a.22 Me 4′-Cl

2′-Cl CF₂H Me 10a.23 H 4′-Cl

5′-Cl CF₂H Me 10a.24 Me 4′-Cl

5′-Cl CF₂H Me 10a.25 H 4′-Cl

2′-Cl CF₃ Me 10a.26 Me 4′-Cl

2′-Cl CF₃ Me 10a.27 H 4′-Cl

5′-Cl CF₃ Me 10a.28 Me 4′-Cl

5′-Cl CF₃ Me 10a.29 H 4′-Cl

2′-Cl CF₃ Me 10a.30 Me 4′-Cl

2′-Cl CF₃ Me 10a.31 H 4′-Cl

5′-Cl CF₃ Me 10a.32 Me 4′-Cl

5′-Cl CF₃ Me 10a.33 H 4′-Cl

2′-Cl CF₃ Me 10a.34 Me 4′-Cl

2′-Cl CF₃ Me 10a.35 H 4′-Cl

5′-Cl CF₃ Me 10a.36 Me 4′-Cl

5′-Cl CF₃ Me 10a.37 H 4′-Cl

2′-Cl CF₃ Me 10a.38 Me 4′-Cl

2′-Cl CF₃ Me 10a.39 H 4′-Cl

5′-Cl CF₃ Me 10a.40 Me 4′-Cl

5′-Cl CF₃ Me 10a.41 H 4′-Cl

2′-Cl CF₃ Me 10a.42 Me 4′-Cl

2′-Cl CF₃ Me 10a.43 H 4′-Cl

5′-Cl CF₃ Me 10a.44 Me 4′-Cl

5′-Cl CF₃ Me 10a.45 H 4′-Cl

2′-Cl CF₃ Me 10a.46 Me 4′-Cl

2′-Cl CF₃ Me 10a.47 H 4′-Cl

5′-Cl CF₃ Me 10a.48 Me 4′-Cl

5′-Cl CF₃ Me

TABLE 11a Compounds of formula IAk (IAk)

Compound Number R₁ R₃ R₄ R₅ R₆ 11a.1 H 4′-Cl

2′-Cl Cl 11a.2 Me 4′-Cl

2′-Cl Cl 11a.3 H 4′-Cl

5′-Cl Cl 11a.4 Me 4′-Cl

5′-Cl Cl 11a.5 H 4′-Cl

2′-Cl Br 11a.6 Me 4′-Cl

2′-Cl Br 11a.7 H 4′-Cl

5′-Cl Br 11a.8 Me 4′-Cl

5′-Cl Br 11a.9 H 4′-Cl

2′-Cl CF₃ 11a.10 Me 4′-Cl

2′-Cl CF₃ 11a.11 H 4′-Cl

5′-Cl CF₃ 11a.12 Me 4′-Cl

5′-Cl CF₃ 11a.13 H 4′-Cl

2′-Cl Cl 11a.14 Me 4′-Cl

2′-Cl Cl 11a.15 H 4′-Cl

5′-Cl Cl 11a.16 Me 4′-Cl

5′-Cl Cl 11a.17 H 4′-Cl

2′-Cl Br 11a.18 Me 4′-Cl

2′-Cl Br 11a.19 H 4′-Cl

5′-Cl Br 11a.20 Me 4′-Cl

5′-Cl Br 11a.21 H 4′-Cl

2′-Cl CF₃ 11a.22 Me 4′-Cl

2′-Cl CF₃ 11a.23 H 4′-Cl

5′-Cl CF₃ 11a.24 Me 4′-Cl

5′-Cl CF₃ 11a.25 H 4′-Cl

2′-Cl Cl 11a.26 Me 4′-Cl

2′-Cl Cl 11a.27 H 4′-Cl

5′-Cl Cl 11a.28 Me 4′-Cl

5′-Cl Cl 11a.29 H 4′-Cl

2′-Cl Br 11a.30 Me 4′-Cl

2′-Cl Br 11a.31 H 4′-Cl

5′-Cl Br 11a.32 Me 4′-Cl

5′-Cl Br 11a.33 H 4′-Cl

2′-Cl CF₃ 11a.34 Me 4′-Cl

2′-Cl CF₃ 11a.35 H 4′-Cl

5′-Cl CF₃ 11a.36 Me 4′-Cl

5′-Cl CF₃ 11a.37 H 4′-Cl

2′-Cl Cl 11a.38 Me 4′-Cl

2′-Cl Cl 11a.39 H 4′-Cl

5′-Cl Cl 11a.40 Me 4′-Cl

5′-Cl Cl 11a.41 H 4′-Cl

2′-Cl Br 11a.42 Me 4′-Cl

2′-Cl Br 11a.43 H 4′-Cl

5′-Cl Br 11a.44 Me 4′-Cl

5′-Cl Br 11a.45 H 4′-Cl

2′-Cl CF₃ 11a.46 Me 4′-Cl

2′-Cl CF₃ 11a.47 H 4′-Cl

5′-Cl CF₃ 11a.48 Me 4′-Cl

5′-Cl CF₃ 11a.49 H 4′-Cl

2′-Cl Cl 11a.50 Me 4′-Cl

2′-Cl Cl 11a.51 H 4′-Cl

5′-Cl Cl 11a.52 Me 4′-Cl

5′-Cl Cl 11a.53 H 4′-Cl

2′-Cl Br 11a.54 Me 4′-Cl

2′-Cl Br 11a.55 H 4′-Cl

5′-Cl Br 11a.56 Me 4′-Cl

5′-Cl Br 11a.57 H 4′-Cl

2′-Cl CF₃ 11a.58 Me 4′-Cl

2′-Cl CF₃ 11a.59 H 4′-Cl

5′-Cl CF₃ 11a.60 Me 4′-Cl

5′-Cl CF₃ 11a.61 H 4′-Cl

2′-Cl Cl 11a.62 Me 4′-Cl

2′-Cl Cl 11a.63 H 4′-Cl

5′-Cl Cl 11a.64 Me 4′-Cl

5′-Cl Cl 11a.65 H 4′-Cl

2′-Cl Br 11a.66 Me 4′-Cl

2′-Cl Br 11a.67 H 4′-Cl

5′-Cl Br 11a.68 Me 4′-Cl

5′-Cl Br 11a.69 H 4′-Cl

2′-Cl CF₃ 11a.70 Me 4′-Cl

2′-Cl CF₃ 11a.71 H 4′-Cl

5′-Cl CF₃ 11a.72 Me 4′-Cl

5′-Cl CF₃

TABLE 12a Compounds of formula IIaa (IIaa)

Compound Number R₁ R₃ R₄ R₅ R₆ 12a.1 H 4′-Cl

2′-Cl CF₂H 12a.2 Me 4′-Cl

2′-Cl CF₂H 12a.3 H 4′-Cl

5′-Cl CF₂H 12a.4 Me 4′-Cl

5′-Cl CF₂H 12a.5 H 4′-Cl

2′-Cl CF₃ 12a.6 Me 4′-Cl

2′-Cl CF₃ 12a.7 H 4′-Cl

5′-Cl CF₃ 12a.8 Me 4′-Cl

5′-Cl CF₃ 12a.9 H 4′-Cl

2′-Cl CF₂H 12a.10 Me 4′-Cl

2′-Cl CF₂H 12a.11 H 4′-Cl

5′-Cl CF₂H 12a.12 Me 4′-Cl

5′-Cl CF₂H 12a.13 H 4′-Cl

2′-Cl CF₃ 12a.14 Me 4′-Cl

2′-Cl CF₃ 12a.15 H 4′-Cl

5′-Cl CF₃ 12a.16 Me 4′-Cl

5′-Cl CF₃ 12a.17 H 4′-Cl

2′-Cl CF₂H 12a.18 Me 4′-Cl

2′-Cl CF₂H 12a.19 H 4′-Cl

5′-Cl CF₂H 12a.20 Me 4′-Cl

5′-Cl CF₂H 12a.21 H 4′-Cl

2′-Cl CF₃ 12a.22 Me 4′-Cl

2°-Cl CF₃ 12a.23 H 4′-Cl

5′-Cl CF₃ 12a.24 Me 4′-Cl

5′-Cl CF₃ 12a.25 H 4′-Cl

2′-Cl CF₂H 12a.26 Me 4′-Cl

2′-Cl CF₂H 12a.27 H 4′-Cl

5′-Cl CF₂H 12a.28 Me 4′-Cl

5′-Cl CF₂H 12a.29 H 4′-Cl

2′-Cl CF₃ 12a.30 Me 4′-Cl

2′-Cl CF₃ 12a.31 H 4′-Cl

5′-Cl CF₃ 12a.32 Me 4′-Cl

5′-Cl CF₃ 12a.33 H 4′-Cl

5′-Cl CF₂H 12a.34 Me 4′-Cl

5′-Cl CF₂H 12a.35 H 4′-Cl

2′-Cl CF₂H 12a.36 Me 4′-Cl

2′-Cl CF₂H 12a.37 H 4′-Cl

5′-Cl CF₃ 12a.38 Me 4′-Cl

5′-Cl CF₃ 12a.39 H 4′-Cl

2′-Cl CF₃ 12a.40 Me 4′-Cl

2′-Cl CF₃ 12a.41 H 4′-Cl

5′-Cl CF₂H 12a.42 Me 4′-Cl

5′-Cl CF₂H 12a.43 H 4′-Cl

2′-Cl CF₂H 12a.44 Me 4′-Cl

2′-Cl CF₂H 12a.45 H 4′-Cl

5′-Cl CF₃ 12a.46 Me 4′-Cl

5′-Cl CF₃ 12a.47 H 4′-Cl

2′-Cl CF₃ 12a.48 Me 4′-Cl

2′-Cl CF₃

TABLE 13a compounds of formula IAm: (IAm)

Com- pound Number R₁ R₃ R₄ R₅ R₆ R₇ R₈ 13a.1 H Cl

6′-H Me Me F 13a.2 Me Cl

6′-H Me Me F 13a.3 H Cl

5′-H Me Me F 13a.4 Me Cl

5′-H Me Me F 13a.5 H Cl

6′-H Me Me F 13a.6 Me Cl

6′-H Me Me F 13a.7 H Cl

5′-H Me Me F 13a.8 Me Cl

5′-H Me Me F 13a.9 H Cl

6′-H Me Me F 13a.10 Me Cl

6′-H Me Me F 13a.11 H Cl

5′-H Me Me F 13a.12 Me Cl

5′-H Me Me F 13a.13 H Cl

6′-H Me Me F 13a.14 Me Cl

6′-H Me Me F 13a.15 H Cl

5′-H Me Me F 13a.16 Me Cl

5′-H Me Me F 13a.17 H Cl

6′-H Me Me F 13a.18 Me Cl

6′-H Me Me F 13a.19 H Cl

5′-H Me Me F 13a.20 Me Cl

5′-H Me Me F 13a.21 H Cl

6′-H Me Me F 13a.22 Me Cl

6′-H Me Me F 13a.23 H Cl

5′-H Me Me F 13a.24 Me Cl

5′-H Me Me F 13a.25 H Cl

6′-H CF₂H Me H 13a.26 Me Cl

6′-H CF₂H Me H 13a.27 H Cl

5′-H CF₂H Me H 13a.28 Me Cl

5′-H CF₂H Me H 13a.29 H Cl

6′-H CF₂H Me H 13a.30 Me Cl

6′-H CF₂H Me H 13a.31 H Cl

5′-H CF₂H Me H 13a.32 Me Cl

5′-H CF₂H Me H 13a.33 H Cl

6′-H CF₂H Me H 13a.34 Me Cl

6′-H CF₂H Me H 13a.35 H Cl

5′-H CF₂H Me H 13a.36 Me Cl

5′-H CF₂H Me H 13a.37 H Cl

6′-H CF₂H Me H 13a.38 Me Cl

6′-H CF₂H Me H 13a.39 H Cl

5′-H CF₂H Me H 13a.40 Me Cl

5′-H CF₂H Me H 13a.41 H Cl

6′-H CF₂H Me H 13a.42 Me Cl

6′-H CF₂H Me H 13a.43 H Cl

5′-H CF₂H Me H 13a.44 Me Cl

5′-H CF₂H Me H 13a.45 H Cl

6′-H CF₂H Me H 13a.46 Me Cl

6′-H CF₂H Me H 13a.47 H Cl

5′-H CF₂H Me H 13a.48 Me Cl

5′-H CF₂H Me H 13a.49 H Cl

6′-H CF₃ Me H 13a.50 Me Cl

6′-H CF₃ Me H 13a.51 H Cl

5′-H CF₃ Me H 13a.52 Me Cl

5′-H CF₃ Me H 13a.53 H Cl

6′-H CF₃ Me H 13a.54 Me Cl

6′-H CF₃ Me H 13a.55 H Cl

5′-H CF₃ Me H 13a.56 Me Cl

5′-H CF₃ Me H 13a.57 H Cl

6′-H CF₃ Me H 13a.58 Me Cl

6′-H CF₃ Me H 13a.59 H Cl

5′-H CF₃ Me H 13a.60 Me Cl

5′-H CF₃ Me H 13a.61 H Cl

6′-H CF₃ Me H 13a.62 Me Cl

6′-H CF₃ Me H 13a.63 H Cl

5′-H CF₃ Me H 13a.64 Me Cl

5′-H CF₃ Me H 13a.65 H Cl

6′-H CF₃ Me H 13a.66 Me Cl

6′-H CF₃ Me H 13a.67 H Cl

5′-H CF₃ Me H 13a.68 Me Cl

5′-H CF₃ Me H 13a.69 H Cl

6′-H CF₃ Me H 13a.70 Me Cl

6′-H CF₃ Me H 13a.71 H Cl

5′-H CF₃ Me H 13a.72 Me Cl

5′-H CF₃ Me H

TABLE 14a compound of formula IAn (IAn)

Compound Number R₁ R₃ R₄ R₅ R₆ 14a.1 H Cl

6′-H CF₃ 14a.2 Me Cl

5′-H CF₃ 14a.3 H Cl

6′-H CF₃ 14a.4 Me Cl

5′-H CF₃ 14a.5 H Cl

6′-H CF₃ 14a.6 Me Cl

5′-H CF₃ 14a.7 H Cl

6′-H CF₃ 14a.8 Me Cl

5′-H CF₃ 14a.9 H Cl

6′-H CF₃ 14a.10 Me Cl

5′-H CF₃ 14a.11 H Cl

6′-H CF₃ 14a.12 Me Cl

5′-H CF₃Tables 15a-17a: Compounds of Formula IIaaa

The invention is further illustrated by the preferred individualcompounds of formula (IIaaa) listed below in Tables 15-17a.Characterising data is given in Table 21a.

TABLE 15 Compounds of formula (IIa) (IIaaa)

Cpd No. R₁ R₃ R_(4A) R₅ A Z1aa.1 H Cl Br H3-difluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1aa.2 Me Cl Br H3-difluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1aa.3 H Br Br H3-difluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1aa.4 Me Br Br H3-difluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1aa.5 H Cl Br H3-trifluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1aa.6 Me Cl Br H3-trifluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1aa.7 H Br Br H3-trifluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1aa.8 Me Br Br H3-trifluoromethyl-1-methyl-1H-pyrazol- 4-yl Z1aa.9 H Cl Br H3-difluoromethyl-1-methyl-pyrrol-4-yl Z1aa.10 Me Cl Br H3-difluoromethyl-1-methyl-pyrrol-4- yl Z1aa.11 H Cl Br H3-difluoromethyl-1-methyl-1H-triazol-4- yl Z1aa.12 Me Cl Br H3-difluoromethyl-1-methyl-1H-triazol-4- yl Z1aa.13 H Cl Br H4-difluoromethyl-2-methyl-thiazol-5-yl Z1aa.14 Me Cl Br H4-difluoromethyl-2-methyl-thiazol-5-yl Z1aa.15 H Cl Br H2-chloro-pyridyl-3-yl Z1aa.16 Me Cl Br H 2-chloro-pyridyl-3-yl Z1aa.17 HCl Br H 2-difluoromethyl-phenyl Z1aa.18 Me Cl Br H2-difluoromethyl-phenyl Z1aa.19 H Cl Br H 2-trifluoromethyl-phenylZ1aa.20 Me Cl Br H 2-trifluoromethyl-phenyl

TABLE 16a Compounds of formula IIab (IIab)

Cpd No. R₁ R₃ R_(4A) R₅ A Z1aa.21 H 4′-Cl 5′-Br 2′-Cl3-difluoromethyl-1-methyl-1H-py- razol-4-yl Z1aa.22 Me 4′-Cl 5′-Br 2′-Cl3-difluoromethyl-1-methyl-1H-py- razol-4-yl Z1aa.23 H 4′-Cl 2′-Br 5′-Cl3-difluoromethyl-1-methyl-1H-py- razol-4-yl Z1aa.24 Me 4′-Cl 2′-Br 5′-Cl3-difluoromethyl-1-methyl-1H-py- razol-4-yl

TABLE 17a Compounds of formula IIac: (IIac)

Cpd No. R₁ R₃ R_(4A) R₅ A Z1aa.25 H Cl 5′-Br 6′-H3-difluoromethyl-1-methyl-1H-py- razol-4-yl Z1aa.26 Me Cl 5-Br 6′-H3-difluoromethyl-1-methyl-1H-py- razol-4-yl Z1aa.27 H Cl 6′-Br 5′-H3-difluoromethyl-1-methyl-1H-py- razol-4-yl Z1aa.28 Me Cl 6′-Br 5′-H3-difluoromethyl-1-methyl-1H-py- razol-4-ylTables 18a-20a: Compounds of formula III

The invention is further illustrated by the preferred individualcompounds of formula (III) listed below in Tables 18-20. Characterisingdata is given in Table 21a.

TABLE 18a Compounds of formula (IIIaa) (IIIaa)

Cpd No. R₁ R₃ R_(4A) R₅ Z2aa.1 H Cl Br H Z2aa.2 Me Cl Br H Z2aa.3 H BrBr H Z2aa.4 Me Br Br H

TABLE 19a Compounds of formula IIIab (IIIab)

Cpd No. R₁ R₃ R_(4A) R₅ Z2aa.5 H 4′-Cl 5′-Br 2′-Cl Z2aa.6 Me 4′-Cl 5′-Br2′-Cl Z2aa.7 H 4′-Cl 2′-Br 5′-Cl Z2aa.8 Me 4′-Cl 2′-Br 5′-Cl

TABLE 20a Compounds of formula IIIac: (IIIac)

Cpd No. R₁ R₃ R_(4A) R₅ Z2aa.9 H Cl 5′-Br 6′-H Z2aa.10 Me Cl 5-Br 6′-HZ2aa.11 H Cl 6′-Br 5′-H Z2aa.12 Me Cl 6′-Br 5′-H

Formulation Examples for Compounds of Formula I Example F-1.1 to F-1.2Emulsifiable Concentrates

Components F-1.1 F-1.2 compound of Tables 1 to 14a 25% 50% calciumdodecylbenzenesulfonate  5%  6% castor oil polyethylene glycol ether  5%— (36 mol ethylenoxy units) tributylphenolpolyethylene glycol ether — 4% (30 mol ethylenoxy units) cyclohexanone — 20% xylene mixture 65% 20%

Emulsions of any desired concentration can be prepared by diluting suchconcentrates with water.

Example F-2 Emulsifiable Concentrate

Components F-2 compound of Tables 1 to 14a 10% octylphenolpolyethyleneglycol ether  3% (4 to 5 mol ethylenoxy units) calciumdodecylbenzenesulfonate  3% castor oil polyglycol ether  4% (36 molethylenoxy units) cyclohexanone 30% xylene mixture 50%

Emulsions of any desired concentration can be prepared by diluting suchconcentrates with water.

Examples F-3.1 to F-3.4 Solutions

Components F-3.1 F-3.2 F-3.3 F-3.4 compound of Tables 1 to 14a 80% 10%5% 95% propylene glycol monomethyl ether 20% — — — polyethylene glycol(relative molecular — 70% — — mass: 400 atomic mass units)N-methylpyrrolid-2-one — 20% — — epoxidised coconut oil — — 1%  5%benzin (boiling range: 160-190°) — — 94%  —

The solutions are suitable for use in the form of microdrops.

Examples F-4.1 to F-4.4 Granulates

Components F-4.1 F-4.2 F-4.3 F-4.4 compound of Tables 1 to 14a 5% 10% 8% 21% kaolin 94%  — 79% 54% highly dispersed silicic acid 1% — 13%  7%attapulgite — 90% — 18%

The novel compound is dissolved in dichloromethane, the solution issprayed onto the carrier and the solvent is then removed by distillationunder vacuum.

Examples F-5.1 and F-5.2 Dusts

Components F-5.1 F-5.2 compound of Tables 1 to 14a 2% 5% highlydispersed silicic acid 1% 5% talcum 97%  — kaolin — 90% 

Ready for use dusts are obtained by intimately mixing all components.

Examples F-6.1 to F-6.3 Wettable Powders

Components F-6.1 F-6.2 F-6.3 compound of Tables 1 to 14a 25%  50% 75%sodium lignin sulfonate 5%  5% — sodium lauryl sulfate 3% —  5% sodiumdiisobutylnaphthalene sulfonate —  6% 10% octylphenolpolyethylene glycolether —  2% — (7 to 8 mol ethylenoxy units) highly dispersed silicicacid 5% 10% 10% kaolin 62%  27% —

All components are mixed and the mixture is thoroughly ground in asuitable mill to give wettable powders which can be diluted with waterto suspensions of any desired concentration.

Example F7 Flowable Concentrate for Seed Treatment

compound of Tables 1 to 14a 40%  propylene glycol 5% copolymer butanolPO/EO 2% tristyrenephenole with 10-20 moles EO 2%1,2-benzisothiazolin-3-one (in the form of a 20% 0.5%   solution inwater) monoazo-pigment calcium salt 5% Silicone oil (in the form of a75% emulsion in water) 0.2%   Water 45.3%  

The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

BIOLOGICAL EXAMPLES Fungicidal Actions Example B-1 Action againstBotrytis cinerea/tomato (Botrytis on tomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application tomato plants are inoculated by spraying a sporesuspension (1×10⁵ conidia/ml) on the test plants. After an incubationperiod of 4 days at 20° C. and 95% r.h. in a growth chamber the diseaseincidence is assessed. Compounds 1.38, 7.27 and 7.38 show good activityin this test (<20% infestation).

Example B-2 Action Against Uncinula necator/Grape (Powdery Mildew onGrape)

5 week old grape seedlings cv. Gutedel are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. One dayafter application, the grape plants are inoculated by shaking plantsinfected with grape powdery mildew above the test plants. After anincubation period of 7 days at 26° C. and 60% r.h. under a light regimeof 14/10 hours (light/dark) the disease incidence is assessed. Compounds1.38, 6.14, 7.27, 7.38, 12.6 and 12.30 show good activity in this test(<20% infestation).

Example B-3 Action Against Puccinia recondita/Wheat (Brownrust on Wheat)

1 week old wheat plants cv. Arina are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. One day afterapplication, the wheat plants are inoculated by spraying a sporesuspension (1×10⁵ uredospores/ml) on the test plants. After anincubation period of 2 days at 20° C. and 95% r.h. the plants are keptin a greenhouse for 8 days at 20° C. and 60% r.h. The disease incidenceis assessed 10 days after inoculation.

Compounds 1.38, 6.14 and 7.38 show good activity in this test (<20%infestation).

Example B-4 Action Against Septoria tritici/Wheat (Septoria Leaf Spot onWheat)

2 week old wheat plants cv. Riband are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. One day afterapplication, wheat plants are inoculated by spraying a spore suspension(10×10⁵ conidia/ml) on the test plants. After an incubation period of 1day at 23° C. and 95% r.h., the plants are kept for 16 days at 23° C.and 60% r.h. in a greenhouse. The disease incidence is assessed 18 daysafter inoculation. Compounds 1.38, 6.14 and 7.38 show good activity inthis test (<20% infestation).

Example B-5 Action Against Pyrenophora teres/Barley (Net Blotch onBarley)

1 week old barley plants cv. Express are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application barley plants are inoculated by spraying a sporesuspension (3×10⁴ conidia/ml) on the test plants. After an incubationperiod of 2 days at 20° C. and 95% r.h. plants are kept for 2 days at20° C. and 60% r.h. in a greenhouse. The disease incidence is assessed 4days after inoculation. Compounds 1.38, 6.14, 7.27, 7.38, 12.6 and 12.30show good activity in this test (<20% infestation).

Example B-6 Action Against Alternaria solani/Tomato (Early Blight onTomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application, the tomato plants are inoculated by spraying a sporesuspension (2×10⁵ conidia/ml) on the test plants. After an incubationperiod of 3 days at 20° C. and 95% r.h. in a growth chamber the diseaseincidence is assessed. Compounds 1.38, 7.27, 7.38, 12.6 and 12.30 showgood activity in this test (<20% infestation).

What is claimed is:
 1. A compound of the formula I

wherein A is A₁

in which R₁₆ is halogen, cyano, nitro, C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; R₁₇ is C₁-C₄alkyl, C₁-C₄halogenalkyl,C₁-C₄halogenalkoxy, C₁-C₄alkoxy-C₁-C₄alkyl orC₁-C₄halogenalkoxy-C₁-C₄alkyl; and R₁₈ is hydrogen, halogen or cyano; R₁and R₂ independently of each other stand for hydrogen, halogen, C₁-C₄alkyl or C₁-C₄ halogenalkyl; Q is Q₁

wherein R₃ is halogen or C₁-C₄ halogenalkyl; R₄ is C₃-C₇ cycloalkylacetynyl, phenyl acetynyl, halogenphenyl acetynyl or halogenphenyl; R₅is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl; R₁₅ is hydrogen or C₃-C₇cycloalkyl; andtautomers/isomers/enantiomers of the compound.
 2. A compound of formulaI according to claim 1, wherein R₁₅ is hydrogen.
 3. A compound offormula I according to claim 1, wherein R₁₆ is C₁-C₄alkyl orC₁-C₄halogenalkyl; R₁₇ is C₁-C₄alkyl; and R₁₈ is hydrogen or halogen. 4.A compound of formula I according to claim 1, wherein R₄ is C₃-C₇cycloalkyl acetynyl, phenyl acetynyl or halogenphenyl acetynyl.
 5. Acompound of formula I according to claim 1, wherein Q is Q_(1A-1)

wherein R₃ is halogen or C₁-C₄ halogenalkyl; R₄ is C₃-C₇ cycloalkylacetynyl, phenyl acetynyl, halogenphenyl acetynyl or halogenphenyl; andR₅ is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl.
 6. A compound of formula I according to claim 1,wherein Q is Q_(1B-1)

wherein R₃ is halogen or C₁-C₄ halogenalkyl; R₄ is C₃-C₇ cycloalkylacetynyl, phenyl acetynyl, halogenphenyl acetynyl or halogenphenyl; andR₅ is hydrogen, halogen, C₁-C₄ alkyl, C₁-C₄ halogenalkyl, phenyl,halogenphenyl, C₃-C₇ cycloalkyl acetynyl, phenyl acetynyl orhalogenphenyl acetynyl.
 7. A method of controlling infestation of usefulplants by phytopathogenic microorganisms, the method comprising:applying an effective amount of a compound of formula I according toclaim 1 or a composition, comprising this compound as active ingredient,to the plants, to parts thereof or the locus thereof.
 8. A compositionfor controlling and protecting against phytopathogenic microorganisms,comprising a compound of formula I according to claim 1 and an inertcarrier.
 9. The method of claim 7, wherein the phytopathogenicmicroorganisms include at least one member selected from the groupconsisting of a Fungi imperfecti class, a Basidiomycetes class, anAscomycetes class, and an Oomycetes class.
 10. The method of claim 7,wherein the phytopathogenic microorganisms include at least one memberselected from the group consisting of a Botrytis species, a Uncinulaspecies, a Puccinia species, a Septoria species, a Pyrenophora species,and an Alternaria species.
 11. The method of claim 10, wherein at leastone of the Botrytis species is Botrytis cinerea, at least one of theUncinula species is Uncinula necator, at least one of the Pucciniaspecies is Puccinia recondita, at least one of the Septoria species isSeptoria tritici, at least one of the Pyrenophora species is Pyrenophorateres, and at least one of the Alternaria species is Alternaria solani.